Dehydrocyclodimerization using UZM-39 aluminosilicate zeolite

ABSTRACT

A new family of coherently grown composites of TUN and IMF zeotypes has been synthesized and shown to be effective catalysts for dehydrocyclodimerization reactions. These zeolites are represented by the empirical formula.
 
Na n M m   n+ R r Q q Al 1-x E x Si y O z  
 
where M represents zinc or a metal or metals from Group 1, Group 2, Group 3 or the lanthanide series of the periodic table, R is an A,Ω-dihalosubstituted paraffin such as 1,4-dibromobutane, Q is a neutral amine containing 5 or fewer carbon atoms such as 1-methylpyrrolidine and E is a framework element such as gallium. The process involves contacting at least one aliphatic hydrocarbon having from 2 to about 6 carbon atoms per molecule with the coherently grown composites of TUN and IMF zeotypes to produce at least one aromatic hydrocarbon.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority from Provisional Application No.61/736,296 filed Dec. 12, 2012, the contents of which are herebyincorporated by reference in its entirety.

FIELD OF THE INVENTION

This invention relates to using a new family of aluminosilicate zeolitesdesignated UZM-39 as the catalytic composite fordehydrocyclodimerization reactions. The zeolite family is represented bythe empirical formula of:Na_(n)M_(m) ^(k+)T_(t)Al_(1-x)E_(x)Si_(y)O_(z)where M represents a metal or metals from zinc or Group 1 (IUPAC 1),Group 2 (IUPAC 2), Group 3 (IUPAC 3) or the lanthanide series of theperiodic table, T is the organic directing agent derived from reactantsR and Q where R is an A,Ω-dihalosubstituted alkane such as1,4-dibromobutane and Q is at least one neutral amine having 6 or fewercarbon atoms such as 1-methylpyrrolidine. E is a framework element suchas gallium.

BACKGROUND OF THE INVENTION

Zeolites are crystalline aluminosilicate compositions which aremicroporous and which are formed from corner sharing AlO₂ and SiO₂tetrahedra. Numerous zeolites, both naturally occurring andsynthetically prepared, are used in various industrial processes.Synthetic zeolites are prepared via hydrothermal synthesis employingsuitable sources of Si, Al and structure directing agents such as alkalimetals, alkaline earth metals, amines, or organoammonium cations. Thestructure directing agents reside in the pores of the zeolite and arelargely responsible for the particular structure that is ultimatelyformed. These species balance the framework charge associated withaluminum and can also serve as space fillers. Zeolites are characterizedby having pore openings of uniform dimensions, having a significant ionexchange capacity, and being capable of reversibly desorbing an adsorbedphase which is dispersed throughout the internal voids of the crystalwithout significantly displacing any atoms which make up the permanentzeolite crystal structure. Zeolites can be used as catalysts forhydrocarbon conversion reactions, which can take place on outsidesurfaces as well as on internal surfaces within the pore.

One particular zeolite, designated TNU-9, was first disclosed by Hong etal. in 2004, (J. Am. Chem. Soc. 2004, 126, 5817-26) and then in a KoreanPatent granted in 2005, KR 480229. This report and patent was followedby a full report of the synthesis in 2007 (J. Am. Chem. Soc. 2007, 129,10870-85). These papers describe the synthesis of TNU-9 from theflexible dicationic structure directing agent,1,4-bis(N-methylpyrrolidinium)butane dibromide in the presence ofsodium. After the structure of TNU-9 was solved (Nature, 2006, 444,79-81), the International Zeolite Association Structure Commission gavethe code of TUN to this zeolite structure type, see Atlas of ZeoliteFramework Types, which is maintained by the International ZeoliteAssociation Structure Commission athttp://www.iza-structure.org/databases/. The TUN structure type wasfound to contain 3 mutually orthogonal sets of channels in which eachchannel is defined by a 10-membered ring of tetrahedrally coordinatedatoms. In addition, 2 different sizes of 10-membered ring channels existin the structure.

Another particular zeolite, IM-5 was first disclosed by Benazzi, et al.in 1996 (FR96/12873; WO98/17581) who describe the synthesis of IM-5 fromthe flexible dicationic structure directing agent,1,5-bis(N-methylpyrrolidinium)pentane dibromide or1,6-bis(N-methylpyrrolidinium)hexane dibromide in the presence ofsodium. After the structure of IM-5 was solved by Baerlocher et al.(Science, 2007, 315, 113-6), the International Zeolite StructureCommission gave the code of IMF to this zeolite structure type, seeAtlas of Zeolite Framework Types. The IMF structure type was also foundto contain three mutually orthogonal sets of channels in which eachchannel is defined by a 10-membered ring of tetrahedrally coordinatedatoms, however, connectivity in the third dimension is interrupted every2.5 nm, therefore diffusion is somewhat limited. In addition, multipledifferent sizes of 10-membered ring channels exist in the structure.

Applicants have successfully prepared a new family of materialsdesignated UZM-39. The topology of the materials is similar to thatobserved for TNU-9 and IM-5. The materials are prepared via the use of amixture of simple commercially available structure directing agents,such as 1,4-dibromobutane and 1-methylpyrrolidine, in concert with Na⁺using the Layered Material Conversion approach to zeolite synthesis(described below). This type of zeolite may be used as a catalyst indehydrocyclodimerization reactions where aliphatic hydrocarbonscontaining from 2 to 6 carbon atoms per molecule are reacted over acatalyst to produce a high yield of aromatics and hydrogen, with a lightends byproduct and a C₂-C₄ recycle product. Processes fordehydrocyclodimerization are known and described in detail in U.S. Pat.No. 4,654,455 and U.S. Pat. No. 4,746,763 which are incorporated byreference.

SUMMARY OF THE INVENTION

As stated, the present invention relates to using a new catalyticcomposite comprising a coherently grown composite of TUN and IMFzeotypes designated UZM-39 as at least a portion of the catalyticcomposite in a process for dehydrocyclodimerization. One embodiment ofthe invention uses a microporous crystalline zeolite having athree-dimensional framework of at least AlO₂ and SiO₂ tetrahedral unitsand an empirical composition in the as synthesized and anhydrous basisexpressed by an empirical formula of:Na_(n)M_(m) ^(k+)T_(t)Al_(1-x)E_(x)Si_(y)O_(z)where “n” is the mole ratio of Na to (Al+E) and has a value fromapproximately 0.05 to 0.5, M represents at least one metal selected fromthe group consisting of zinc, Group 1 (IUPAC 1), Group 2 (IUPAC 2),Group 3 (IUPAC 3), and the lanthanide series of the periodic table, andany combination thereof, “m” is the mole ratio of M to (Al+E) and has avalue from 0 to 0.5, “k” is the average charge of the metal or metals M,T is the organic structure directing agent or agents derived fromreactants R and Q where R is an A,Ω-dihalogen substituted alkane havingfrom 3 to 6 carbon atoms and Q is at least one neutral monoamine having6 or fewer carbon atoms, “t” is the mole ratio of N from the organicstructure directing agent or agents to (Al+E) and has a value of fromabout 0.5 to about 1.5, E is an element selected from the groupconsisting of gallium, iron, boron and combinations thereof, “x” is themole fraction of E and has a value from 0 to about 1.0, “y” is the moleratio of Si to (Al+E) and varies from greater than 9 to about 25 and “z”is the mole ratio of O to (Al+E) and has a value determined by theequation:z=(n+k·m+3+4·y)/2and is characterized in that it has TUN regions and IMF regions that arecoherently aligned so that the [010]_(TUN) zone axis and the [001]_(IMF)zone axis are parallel to each other and there is continuity of crystalplanes of type (002)_(TUN) and (060)_(IMF), where the indexing isreferred to monoclinic C_(2/m) and orthorhombic C_(mcm) unit cells forTUN and IMF respectively.

The microporous crystalline zeolite may also be described as having athree-dimensional framework of at least AlO₂ and SiO₂ tetrahedral unitsand an empirical composition in the as synthesized and anhydrous basisexpressed by an empirical formula of:Na_(n)M_(m) ^(k+)T_(t)Al_(1-x)E_(x)Si_(y)O_(z)where “n” is the mole ratio of Na to (Al+E) and has a value fromapproximately 0.05 to 0.5, M represents a metal or metals from Group 1(IUPAC 1), Group 2 (IUPAC 2), Group 3 (IUPAC 3), the lanthanide seriesof the periodic table or zinc, “m” is the mole ratio of M to (Al+E) andhas a value from 0 to 0.5, “k” is the average charge of the metal ormetals M, T is the organic structure directing agent or agents derivedfrom reactants R and Q where R is an A,Ω-dihalogen substituted alkanehaving between 3 and 6 carbon atoms and Q is at least one neutralmonoamine having 6 or fewer carbon atoms, “t” is the mole ratio of Nfrom the organic structure directing agent or agents to (Al+E) and has avalue of from 0.5 to 1.5, E is an element selected from the groupconsisting of gallium, iron, boron and combinations thereof, “x” is themole fraction of E and has a value from 0 to about 1.0, “y” is the moleratio of Si to (Al+E) and varies from greater than 9 to about 25 and “z”is the mole ratio of O to (Al+E) and has a value determined by theequation:z=(n+k·m+3+4·y)/2and the zeolite is characterized in that it has the x-ray diffractionpattern having at least the d-spacings and intensities set forth inTable A1

TABLE A1 2θ d (Å) I/Io % 7.17-7.21 12.25-12.31 vw-m  7.5-8.1*11.78-10.91 w-m 8.88 9.95 m 9.17 9.63 w-m 12.47-12.62 7.09-7.00 w-m17.7  5.01 vw-m 22.8-23.2 3.90-3.83 vs 23.39-23.49 3.80-3.78 m-s25.01-25.31 3.56-3.52 m 28.74-29.25 3.10-3.05 w-m 45.08-45.29 2.01-2.00w *composite peak consisting of multiple overlapping reflectionsThe zeolite is thermally stable up to a temperature of greater than 600°C. in one embodiment and at least 800° C. in another embodiment.

The zeolite of the catalytic composite used in the process may beprepared by a process comprising forming a reaction mixture containingreactive sources of Na, R, Q, Al, Si, seeds of a layered material L andoptionally E and/or M and heating the reaction mixture at a temperatureof about 150° C. to about 200° C., about 155° C. to about 190° C., orabout 160° C. to about 180° C., for a time sufficient to form thezeolite. L does not have the same zeotype as the UZM-39 coherently growncomposite. The reaction mixture has a composition expressed in terms ofmole ratios of the oxides of:a-bNa₂O:bM_(n/2)O:cRO:dQ:1-eAl₂O₃ :eE₂O₃ :fSiO₂ :gH₂Owhere “a” has a value of about 10 to about 30, “b” has a value of 0 toabout 30, “c” has a value of about 1 to about 10, “d” has a value ofabout 2 to about 30, “e” has a value of 0 to about 1.0, “f” has a valueof about 30 to about 100, “g” has a value of about 100 to about 4000.Additionally, the reaction mixture comprises from about 1 to about 10wt.-% of seed zeolite L based on the amount of SiO₂ in the reactionmixture, e.g., if there is 100 g of SiO₂ in the reaction mixture, fromabout 1 to about 10 g of seed zeolite L would be added to the reactionmixture. With this number of reactive reagent sources, many orders ofaddition can be envisioned. Typically, the aluminum reagent is dissolvedin the sodium hydroxide prior to adding the silica reagents. As can beseen in the examples, reagents R and Q can be added together orseparately in many different orders of addition.

The invention involves a process of dehydrocyclodimerization using theabove-described zeolite as at least a portion of the catalyticcomposite. The process comprises reacting aliphatic hydrocarbonscontaining from 2 to about 6 carbon atoms per molecule over a catalystto produce a high yield of aromatics and hydrogen, with a light endsbyproduct and a C₂-C₄ recycle product. The dehydrocyclodimerizationreaction is carried out at temperatures in excess of 300° C. (572° F.),using the dual functional catalyst containing acidic and dehydrogenationcomponents. At least the acidic function is provided by the zeolitedescribed above which promotes the oligomerization and aromatizationreactions. Optionally, a non-noble metal component may also be used topromote the dehydrogenation function.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an XRD pattern of the UZM-39 zeolite formed in Example 1. Thispattern shows the UZM-39 zeolite in the as-synthesized form.

FIG. 2 is also an XRD pattern of the UZM-39 zeolite formed in Example 1.This pattern shows the UZM-39 zeolite after calcination.

FIG. 3 is an XRD pattern of the UZM-39 zeolite formed in Example 16.This pattern shows the UZM-39 zeolite in the as-synthesized form.

FIG. 4 is also an XRD pattern of the UZM-39 zeolite formed in Example16. This pattern shows the UZM-39 zeolite in the H⁺ form.

FIG. 5 is an XRD pattern of the UZM-39 zeolite formed in Example 28.This pattern shows the UZM-39 zeolite in the as-synthesized form.

FIG. 6 is also an XRD pattern of the UZM-39 zeolite formed in Example28. This pattern shows the UZM-39 zeolite in the H⁺ form.

FIG. 7 shows the results of high-resolution scanning electron microscopycharacterization of the UZM-39 product of Example 1. The electronmicrograph shows that UZM-39 forms in lathes which assemble intorectangular rod particles, often with a starburst cluster arrangement.The starburst cluster rods of UZM-39 can be seen in the scanningelectron microscopy results of FIG. 7.

FIG. 8 shows the results of high-resolution scanning electron microscopycharacterization of a different UZM-39, that of the product of Example18. The electron micrograph also shows lathes assembled into rectangularrod particles with a number of starburst cluster arrangements.

FIG. 9 shows a wireframe representation of the TUN framework in the ACplane (left). Each vertex is a T-site and in the middle of each stick isan oxygen atom. A wireframe representation of the IMF framework in theAB plane is shown to the right. Along these projections, both the TUNand IMF frameworks contain nearly identical projections of chains of5-rings connected by 6-rings and 10-ring channels.

FIG. 10 shows the results of transmission electron microscopycharacterization of the UZM-39 product of Example 17 using highresolution imaging and computed optical diffractograms. The results showthat UZM-39 is comprised of a coherently grown composite structure ofTUN and IMF zeotypes.

FIG. 11 is an electron diffraction analysis of the cross sectioned rodparticle of

FIG. 10 and shows that from what appears to be a single-crystallinezeolite particle, areas that index to [010] zone axis of TUN and to[001] zone axis of IMF are found. The TUN regions and IMF regions arecoherently aligned.

FIG. 12 is a plot of the low angle region in XRD analysis of materialsshowing that small percentages of IMF can be determined in sampleslargely consisting of TUN.

FIG. 13 is a plot of the low angle region in XRD analysis of materialsshowing that small percentages of TUN can be determined in sampleslargely consisting of IMF.

DETAILED DESCRIPTION OF THE INVENTION

Applicants have prepared a catalytic component suitable for catalyzingdehydrocyclodimerization reactions where at least a portion of thecatalytic component is an aluminosilicate zeolite whose topologicalstructure is related to TUN as described in Atlas of Zeolite FrameworkTypes, which is maintained by the International Zeolite AssociationStructure Commission at http://www.iza-structure.org/databases/, themember of which has been designated TNU-9. As will be shown in detail,UZM-39 is different from TNU-9 in a number of its characteristicsincluding its x-ray diffraction pattern (XRD). UZM-39 is also related toIMF as described in the Atlas of Zeolite Framework Types, the member ofwhich has been designated IM-5. As will be shown in detail, UZM-39 isdifferent from TNU-9 and IM-5 in a number of its characteristicsincluding its x-ray diffraction pattern. The instant microporouscrystalline zeolite (UZM-39) has an empirical composition in the assynthesized and anhydrous basis expressed by an empirical formula of:Na_(n)M_(m) ^(k+)T_(t)Al_(1-x)E_(x)Si_(y)O_(z)where “n” is the mole ratio of Na to (Al+E) and has a value fromapproximately 0.05 to 0.5, M represents a metal or metals selected fromthe group consisting of zinc, Group 1 (IUPAC 1), Group 2 (IUPAC 2),Group 3 (IUPAC 3), the lanthanide series of the periodic table, and anycombination thereof, “m” is the mole ratio of M to (Al+E) and has avalue from 0 to 0.5, “k” is the average charge of the metal or metals M,T is the organic structure directing agent or agents derived fromreactants R and Q where R is an A,Ω-dihalogen substituted alkane havingbetween 3 and 6 carbon atoms and Q is at least one neutral monoaminehaving 6 or fewer carbon atoms, “t” is the mole ratio of N from theorganic structure directing agent or agents to (Al+E) and has a value offrom 0.5 to 1.5, E is an element selected from the group consisting ofgallium, iron, boron and combinations thereof, “x” is the mole fractionof E and has a value from 0 to about 1.0, “y” is the mole ratio of Si to(Al+E) and varies from greater than 9 to about 25 and “z” is the moleratio of O to (Al+E) and has a value determined by the equation:z=(n+k·m+3+4·y)/2where M is only one metal, then the weighted average valence is thevalence of that one metal, i.e. +1 or +2. However, when more than one Mmetal is present, the total amount of:M_(m) ^(k)+M_(m1) ^((k1)+)+M_(m2) ^((k2)+)+M_(m3) ^((k3)+)+M_(m4)^((k4)+)+ . . .and the weighted average valence “k” is given by the equation:

$k = \frac{{m\;{1 \cdot k}\; 1} + {m\;{2 \cdot k}\; 2} + {m\;{3 \cdot k}\; 3\mspace{14mu}\ldots}}{{m\; 1} + {m\; 2} + {m\; 3\mspace{14mu}\ldots}}$

The microporous crystalline zeolite, UZM-39, may be synthesized by ahydrothermal crystallization of a reaction mixture prepared by combiningreactive sources of sodium, organic structure directing agent or agentsT, aluminum, silicon, seeds of a layered material L, and optionally E,M, or both. The sources of aluminum include but are not limited toaluminum alkoxides, precipitated aluminas, aluminum metal, aluminumhydroxide, sodium aluminate, aluminum salts and alumina sols. Specificexamples of aluminum alkoxides include, but are not limited to aluminumsec-butoxide and aluminum ortho isopropoxide. Sources of silica includebut are not limited to tetraethylorthosilicate, colloidal silica,precipitated silica and alkali silicates. Sources of sodium include butare not limited to sodium hydroxide, sodium aluminate, sodium bromide,and sodium silicate.

T is the organic structure directing agent or agents derived fromreactants R and Q where R is an A,Ω-dihalogen substituted alkane havingbetween 3 and 6 carbon atoms and Q comprises at least one neutralmonoamine having 6 or fewer carbon atoms. R may be an A,Ω-dihalogensubstituted alkane having between 3 and 6 carbon atoms selected from thegroup consisting of 1,3-dichloropropane, 1,4-dichlorobutane,1,5-dichloropentane, 1,6-dichlorohexane, 1,3-dibromopropane,1,4-dibromobutane, 1,5-dibromopentane, 1,6-dibromohexane,1,3-diiodopropane, 1,4-diiodobutane, 1,5-diiodopentane, 1,6-diiodohexaneand combinations thereof. Q comprises at least one neutral monoaminehaving 6 or fewer carbon atoms such as 1-ethylpyrrolidine,1-methylpyrrolidine, 1-ethylazetidine, 1-methylazetidine, triethylamine,diethylmethylamine, dimethylethylamine, trimethylamine,dimethylbutylamine, dimethylpropylamine, dimethylisopropylamine,methylethylpropylamine, methylethylisopropylamine, dipropylamine,diisopropylamine, cyclopentylamine, methylcyclopentylamine,hexamethyleneimine. Q may comprise combinations of multiple neutralmonoamines having 6 or fewer carbon atoms.

L comprises at least one seed of a layered zeolite. Suitable seedzeolites are layered materials that are microporous zeolites withcrystal thickness in at least one dimension of less than about 30 toabout 50 nm. The microporous materials have pore diameters of less thanabout 2 nm. The seed layered zeolite is of a different zeotype than theUZM-39 coherently grown composite being synthesized. Examples ofsuitable layered materials include but are not limited to UZM-4M (U.S.Pat. No. 6,776,975), UZM-5 (U.S. Pat. No. 6,613,302), UZM-8 (U.S. Pat.No. 6,756,030), UZM-8HS (U.S. Pat. No. 7,713,513), UZM-26(US-2010-0152023-A1), UZM-27 (U.S. Pat. No. 7,575,737), BPH, FAU/EMTmaterials, *BEA or zeolite Beta, members of the MWW family such asMCM-22P and MCM-22, MCM-36, MCM-49, MCM-56, ITQ-1, ITQ-2, ITQ-30, ERB-1,EMM-10P and EMM-10, SSZ-25, and SSZ-70 as well as smaller microporousmaterials such as PREFER (pre ferrierite), NU-6 and the like.

M represents at least one exchangeable cation of a metal or metals fromGroup 1 (IUPAC 1), Group 2 (IUPAC 2), Group 3 (IUPAC 3), or thelanthanide series of the periodic table and or zinc. Specific examplesof M include but are not limited to lithium, potassium, rubidium,cesium, magnesium, calcium, strontium, barium, zinc, yttrium, lanthanum,gadolinium, and mixtures thereof. Reactive sources of M include, but arenot limited to, the group consisting of halide, nitrate, sulfate,hydroxide, or acetate salts. E is an element selected from the groupconsisting of gallium, iron, boron and combinations thereof, andsuitable reactive sources include, but are not limited to, boric acid,gallium oxyhydroxide, gallium sulfate, gallium nitrate, ferric sulfate,ferric nitrate, ferric chloride and mixtures thereof.

The reaction mixture containing reactive sources of the desiredcomponents can be described in terms of molar ratios of the oxides bythe formula:a-bNa₂O:bM_(n/2)O:cRO:dQ:1-eAl₂O₃ :eE₂O₃ :fSiO₂:gH₂Owhere “a” has a value of about 10 to about 30, “b” has a value of 0 toabout 30, “c” has a value of about 1 to about 10, “d” has a value ofabout 2 to about 30, “e” has a value of 0 to about 1.0, “f” has a valueof about 30 to about 100, “g” has a value of about 100 to about 4000.Additionally in the reaction mixture is from about 1 to about 10 wt.-%of seed zeolite L based on the amount of SiO₂ in the reaction, e.g., ifthere is 100 g of SiO₂ in the reaction mixture, from about 1 to about 10g of seed zeolite L would be added. The examples demonstrate a number ofspecific orders of addition for the reaction mixture which lead toUZM-39. However, as there are at least 6 starting materials, many ordersof addition are possible. For example, the seed crystals L can be addedas the last ingredient to the reaction mixture, to the reactive Sisource, or at other suitable points. Also, if alkoxides are used, it ispreferred to include a distillation or evaporative step to remove thealcohol hydrolysis products. While the organic structure directingagents R and Q can be added separately or together to the reactionmixture at a number of points in the process, it is preferred to mix Rand Q together at room temperature and add the combined mixture to acooled mixture of reactive Si, Al and Na sources maintained at 0-10° C.Alternatively, the mixture of R and Q, after mixing at room temperature,could be cooled and the reactive sources of Si, Al and Na added to theorganic structure directing agent mixture while maintaining atemperature of 0-10° C. In an alternative embodiment, the reagents R andQ could be added, separately or together, to the reaction mixture atroom temperature.

The reaction mixture is then reacted at a temperature of about 150° C.to about 200° C., about 155° C. to about 190° C., or about 160° C. toabout 180° C., for a period of about 1 day to about 3 weeks andpreferably for a time of about 3 days to about 12 days in a stirred,sealed reaction vessel under autogenous pressure. After crystallizationis complete, the solid product is isolated from the heterogeneousmixture by means such as filtration or centrifugation, and then washedwith deionized water and dried in air at ambient temperature up to about100° C.

The as-synthesized coherently grown composite of TUN and IMF zeotypes,UZM-39, is characterized by the x-ray diffraction pattern, having atleast the d-spacings and relative intensities set forth in Tables A1-A3below. Diffraction patterns herein were obtained using a typicallaboratory powder diffractometer, utilizing the K_(α) line of copper; CuK alpha. From the position of the diffraction peaks represented by theangle 2theta, the characteristic interplanar distances d_(hk1) of thesample can be calculated using the Bragg equation. The intensity iscalculated on the basis of a relative intensity scale attributing avalue of 100 to the line representing the strongest peak on the X-raydiffraction pattern, and then: very weak (vw) means less than 5; weak(w) means less than 15; medium (m) means in the range 15 to 50; strong(s) means in the range 50 to 80; very strong (vs) means more than 80.Intensities may also be shown as inclusive ranges of the above. TheX-ray diffraction patterns from which the data (d spacing and intensity)are obtained are characterized by a large number of reflections some ofwhich are broad peaks or peaks which form shoulders on peaks of higherintensity. Some or all of the shoulders may not be resolved. This may bethe case for samples of low crystallinity, of particular coherentlygrown composite structures or for samples with crystals which are smallenough to cause significant broadening of the X-rays. This can also bethe case when the equipment or operating conditions used to produce thediffraction pattern differ significantly from those used in the presentcase.

The X-ray diffraction pattern for UZM-39 contains many peaks. Examplesof the x-ray diffraction patterns for various as-synthesized UZM-39products are shown in FIGS. 1, 3, and 5. Those peaks characteristic ofUZM-39 are shown in Tables A1-A3 for various coherently grown compositestructures. Additional peaks, particularly those of very weak intensity,may also be present. All peaks of medium or higher intensity present inthe UZM-39 family of coherently grown composite structures arerepresented in at least Table A3.

Table A1 contains selected d-spacings and relative intensities of theUZM-39 X-ray diffraction pattern. The relative intensities are shown asa range covering UZM-39 materials with varying relative amounts of TUNand IMF zeotypes.

TABLE A1 2θ d (Å) I/Io % 7.17-7.21 12.25-12.31 vw-m  7.5-8.1*11.78-10.91 w-m 8.88 9.95 M 9.17 9.63 w-m 12.47-12.62 7.09-7.00 w-m17.7  5.01 vw-m 22.8-23.2 3.90-3.83 Vs 23.39-23.49 3.80-3.78 m-s25.01-25.31 3.56-3.52 M 28.74-29.25 3.10-3.05 w-m 45.08-45.29 2.01-2.00W *composite peak consisting of multiple overlapping reflections

The zeolite may be further characterized by the x-ray diffractionpattern having at least the d-spacings and intensities set forth inTable A2 where the d-spacings and intensities are provided at differentrelative concentrations of the components of the coherently growncomposite structure.

TABLE A2 I II III high TUN, low IMF med TUN, med IMF low TUN, high IMF2-Theta d(†) I/Io % 2-Theta d(†) I/Io % 2-Theta d(†) I/Io %  7.21 12.25 w-m  7.17 12.31  w-m 7.21 12.25  vw 7.5-8.1* 11.78-10.91 w-m 7.5-8.1*11.78-10.91 w-m 7.5-8.1* 11.78-10.91 w-m  8.88 9.95 m  8.88 9.95 s 8.889.95 m  9.17 9.63 m  9.16 9.65 m 9.17** 9.63 w-m   9.34** 9.46 vw-w 9.30 9.50 m 9.33 9.47 m 12.62 7.00 w 12.50 7.08 w-m 12.47 7.09 w-m17.70 5.01 vw-w 17.72 5.00 w-m 17.70 5.01 vw-w 19.20 4.62 w-m 22.8-23.2*3.90-3.83 vs 18.71 4.74 w-m 22.89 3.88 vs 23.43 3.79 s 22.55 3.94 m23.49 3.78 m 25.12 3.54 m 23.03 3.86 vs 25.31 3.52 m 28.74-29.25*3.10-3.05 w-m 23.39 3.80 s 29.10 3.07 w 45.29 2.00 w 25.01 3.56 m 45.082.01 w 28.76 3.10 w-m 45.08 2.01 w *composite peak consisting ofmultiple overlapping reflections **typically a shoulder

The zeolite may be yet further characterized by the x-ray diffractionpattern having at least the d-spacings and intensities set forth inTable A3 where the d-spacings and intensities are provided at differentrelative concentrations of the components of the coherently growncomposite structure.

TABLE A3 I II III high TUN, low IMF med TUN, med IMF low TUN, high IMF2-Theta d(†) I/Io % 2-Theta d(†) I/Io % 2-Theta d(†) I/Io % 7.21 12.25 w-m 7.17 12.31  w-m 7.21 12.22  vw 7.5-8.1* 11.78-10.91 w-m 7.5-8.1*11.78-10.91 w-m 7.5-8.1* 11.78-10.91 w-m 8.88 9.95 m 8.88 9.95 m-s 8.889.95 m 9.17 9.63 m 9.16 9.65 m 9.17** 9.63 w-m 9.34** 9.46 vw-w 9.309.50 m 9.33 9.47 m 9.98 8.85 vw 12.50 7.08 w-m 12.47 7.09 w-m 11.68 7.57vw 15.27 5.80 vw-w 12.85 6.88 vw 12.62 7.00 w 15.58 5.68 w 14.62 6.05vw-w 13.69 6.46 vw-w 17.70 5.01 vw-w 15.27 5.80 w 15.33 5.77 vw-w 18.724.74 vw-m 15.57 5.68 w 16.48 5.37 vw-w 19.28 4.60 w 16.60 5.34 w 17.015.20 vw 22.61** 3.93 w-m 17.70 5.01 vw-w 17.70 5.01 vw-w 22.8-23.2*3.90-3.83 vs 18.71 4.74 w-m 19.20 4.62 w-m 23.43 3.79 s 19.30 4.59 w21.59 4.11 vw-w 24.20 3.68 m 22.55 3.94 m 22.61** 3.93 w-m 25.12 3.54 m22.86** 3.89 m-s 22.89 3.88 vs 26.34 3.38 w-m 23.03 3.86 vs 23.49 3.78 m26.75 3.33 w-m 23.39 3.80 s 23.93 3.72 vw-w 28.74-29.25* 3.10-3.05 w-m24.17 3.68 m 24.13 3.68 m 35.72 2.51 vw-w 25.01 3.56 m 24.64 3.61 w45.29 2.00 w 26.19 3.40 vw-w 24.93 3.57 w 45.62-47.19* 1.99-1.92 vw-w26.68 3.34 w-m 25.31 3.52 m 28.76 3.10 w-m 26.62 3.35 w 35.72 2.51 vw-w29.10 3.07 w 45.08 2.01 w 35.72 2.51 vw-w 45.62-47.19* 1.99-1.92 vw-w45.08 2.01 w 45.62-47.19* 1.99-1.92 vw-w *composite peak consisting ofmultiple overlapping reflections **Typically a shoulder

In Tables A2 and A3, the term “high” refers to about 60 to about 95mass-% of the specified component, the term “med” refers to about 25 toabout 70 mass-% of the specified component, and the term “low” refers toabout 5 to about 40 mass-% of the specified component. Some peaks may beshoulders on more intense peaks, and some peaks may be a composite peakconsisting of multiple overlapping reflections.

The UZM-39 material is thermally stable up to a temperature of at least600° C. and in another embodiment, up to at least 800° C. The UZM-39material may have a micropore volume as a percentage of total porevolume of greater than 60%.

Characterization of the UZM-39 product by high-resolution scanningelectron microscopy shows that the UZM-39 forms in lathes which assembleinto rectangular rod particles, often with a starburst clusterarrangement. The starburst cluster rods of UZM-39 can be seen in thescanning electron microscopy results for two particular UZM-39 productsin FIG. 7 and in FIG. 8.

UZM-39 is a coherently grown composite structure of TUN and IMFzeotypes. By coherently grown composite structure is meant that bothstructures are present in a major portion of the crystals in a givensample. This coherently grown composite structure is possible when thetwo zeotypic structures have nearly identical spacial arrangements ofatoms along at least a planar projection of their crystal structure andpossess similar pore topologies. FIG. 9 shows a wireframe representationof the TUN framework in the AC plane (left). Each vertex is atetrahedral site (or T-site) and in the middle of each stick is acorner-shared oxygen atom. A wireframe representation of the IMFframework in the AB plane is shown on the right of FIG. 9. Along theseprojections, both the TUN and IMF zeotypes contain nearly identicalprojections of chains of 5-rings connected by 6-rings and 10-rings whichform channels running perpendicular to the plane.

As both the TUN and IMF zeotypes are 3-dimensional 10-ring zeolites andhave nearly identical projections in one plane, the two structures canthereby coherently grow off crystals of the other structure withinterfaces at the compatible planes to form a coherently grown compositestructure.

A coherently grown composite structure is not a physical mixture of thetwo molecular sieves. Electron diffraction, transmission electronmicroscopy and x-ray diffraction analysis are employed to show that amaterial is a coherently grown composite structure instead of a physicalmixture. Usually the combination of electron diffraction and TEM imagingis most definitive in determining whether one has produced a coherentlygrown composite structure because it provides direct evidence of theexistence of both structures within one crystal.

Since the coherently grown composite structure zeolites of thisinvention can have varying amounts of the two structure types, it is tobe understood that the relative intensity and line width of some of thediffraction lines will vary depending on the amount of each structurepresent in the coherently grown composite structure. Although the degreeof variation in the x-ray powder diffraction patterns is theoreticallypredictable for specific structures, the more likely mode of acoherently grown composite structure is random in nature and thereforedifficult to predict without the use of large hypothetical models asbases for calculation.

Unlike a physical mixture of TNU-9 and IM-5, transmission electronmicroscopy (TEM) analysis using high resolution imaging and computedoptical diffractograms shows that UZM-39 is comprised of a coherentlygrown composite structure of TUN and IMF zeotypes.

In FIG. 10, TEM analysis of a cross sectioned rod particle from theproduct of Example 17 shows that areas with TUN and IMF structure occuras coherent sub-regions within an effectively single-crystalline zeoliteparticle. On the left side of FIG. 11, electron diffraction analysis ofthe left side of the particle shown in FIG. 10 shows an electrondiffraction pattern which can be indexed to the 002 plane of TUN. On theright side of FIG. 11, the electron diffraction pattern from the rightside of the particle shown in FIG. 10 is shown. This pattern can beindexed to the 060 plane of IMF. The TUN regions and IMF regions arecoherently aligned such that the [010]_(TUN) zone axis and the[001]_(IMF) zone axis are parallel to each other and there is continuityof crystal planes of type (002)_(TUN) and (060)_(IMF), where theindexing is referred to monoclinic C_(2/m) and orthorhombic C_(mcm) unitcells for TUN and IMF respectively (details of structures found on IZAwebsite). In spite of the presence of the two zeotypes in differentportions of the particle, the image does not show any distinct boundarydelineating separate crystals of TUN and IMF, indicating that theparticle is a coherently grown composite.

Additionally, UZM-39 zeolite can be characterized by Rietveld analysisof the XRD pattern. Rietveld analysis is a least-squares approachdeveloped by Rietveld (Journal of Applied Crystallography 1969, 2:65-71) to refine a theoretical line XRD profile until it matches themeasured XRD pattern as closely as possible and is the preferred methodof deriving structural information from samples such as UZM-39 whichcontain strongly overlapping reflections. It is often used to quantifythe amounts of two different phases in a XRD diffractogram. The accuracyof the Rietveld method is determined by parameters such as crystallitesize (peak broadening), peak shape function, lattice unit cell constantsand background fits. For the samples shown in the examples, applicantshave determined the error in the reported value to be ±5% under theconditions used. Applicants have also determined that the Rietveld modelused was unable to quantify the amounts of minority composite structurephase components at values less than 10%, but visually, amounts of theminority components can be seen at levels greater than 5% by comparingagainst the model patterns. Table 1 shows Rietveld refinement results onvarious UZM-39 samples from the examples and shows that UZM-39 containsgreater than 0 and less than 100 wt. % IMF zeotype and less than 100 wt.% and greater than 0 wt. % TUN zeotype. In another embodiment, UZM-39contains greater than 5 and less than 95 wt. % IMF zeotype and less than95 wt. % and greater than 5 wt. % TUN zeotype, and in yet anotherembodiment, UZM-39 contains greater than 10 and less than 90 wt. % IMFzeotype and less than 90 wt. % and greater than 10 wt. % TUN zeotype. Ascan be seen in Table 1 and examples, a wide range of coherently growncomposite structures are possible by modifying the synthesis conditions.

As synthesized, the UZM-39 material will contain some exchangeable orcharge balancing cations in its pores. These exchangeable cations can beexchanged for other cations, or in the case of organic cations, they canbe removed by heating under controlled conditions. It is also possibleto remove some organic cations from the UZM-39 zeolite directly by ionexchange. The UZM-39 zeolite may be modified in many ways to tailor itfor use in a particular application. Modifications include calcination,ion-exchange, steaming, various acid extractions, ammoniumhexafluorosilicate treatment, or any combination thereof, as outlinedfor the case of UZM-4M in U.S. Pat. No. 6,776,975 B1 which isincorporated by reference in its entirety. Conditions may be more severethan shown in U.S. Pat. No. 6,776,975. Properties that are modifiedinclude porosity, adsorption, Si/Al ratio, acidity, thermal stability,and the like.

After calcination, ion-exchange and calcination and on an anhydrousbasis, the microporous crystalline zeolite UZM-39 has athree-dimensional framework of at least AlO₂ and SiO₂ tetrahedral unitsand an empirical composition in the hydrogen form expressed by anempirical formula ofM1_(a) ^(N+)Al_((1-x))E_(x)Si_(y′)O_(z″)where M1 is at least one exchangeable cation selected from the groupconsisting of alkali, alkaline earth metals, rare earth metals, ammoniumion, hydrogen ion and combinations thereof, “a” is the mole ratio of M1to (Al+E) and varies from about 0.05 to about 50, “N” is the weightedaverage valence of M1 and has a value of about +1 to about +3, E is anelement selected from the group consisting of gallium, iron, boron, andcombinations thereof, x is the mole fraction of E and varies from 0 to1.0, y′ is the mole ratio of Si to (Al+E) and varies from greater thanabout 9 to virtually pure silica and z″ is the mole ratio of O to (Al+E)and has a value determined by the equation:z″=(a·N+3+4·y′)/2

In the hydrogen form, after calcination, ion-exchange and calcination toremove NH₃, UZM-39 displays the XRD pattern shown in Table B1-B3. Thosepeaks characteristic of UZM-39 are shown in Tables B1-B3 for variouscoherently grown composite structures. Additional peaks, particularlythose of very weak intensity, may also be present. All peaks of mediumor higher intensity present in the UZM-39 family of coherently growncomposite structures are represented in at least Tables B3.

Table B1 contains selected d-spacings and relative intensities of thehydrogen form of UZM-39 X-ray diffraction pattern. The relativeintensities are shown as a range covering UZM-39 materials with varyingrelative amounts of TUN and IMF zeotypes.

TABLE B1 2θ d (Å) I/Io % 7.11-7.16 12.42-12.25 vw-m  7.5-8.1*11.78-10.91 m-s  8.84  10.00 m-s 9.06-9.08 9.75-9.73 w-m  9.24 9.56 vw-m12.46-12.53 7.10-7.06 w-m 22.56 3.94 vw-m 22.75-23.2 3.90-3.83 vs 23.403.80 m-s 24.12-24.23 3.69-3.67 w-m 24.92-25.37 3.57-3.51 m 28.71-29.273.11-3.05 w-m 45.32-45.36 2.00 w *composite peak consisting of multipleoverlapping reflections

The zeolite may be further characterized by the x-ray diffractionpattern having at least the d-spacings and intensities set forth inTable B2 where the d-spacings and intensities are provided at differentrelative concentrations of the components of the coherently growncomposite structure.

TABLE B2 A B C high TUN, low IMF med TUN, med IMF low TUN, high IMF2-Theta d(†) I/Io % 2-Theta d(†) I/Io % 2-Theta d(†) I/Io %  7.12 12.40w-m 7.11 12.42  w-m 7.16 12.25 vw-w 7.5-8.1* 11.78-10.91 m 7.5-8.1*11.78-10.91 m-s 7.5-8.1* 11.78-10.91 m-s  8.84 10.00 m-s 8.84 10.00  m-s8.84 10.00 m-s  9.06 9.75 m 9.08 9.73 m 9.06** 9.75 w   9.24** 9.56 vw-w9.24 9.56 m 9.24 9.56 m 12.53 7.06 w 12.48 7.09 m 12.46 7.10 m 22.893.88 vs 22.56** 3.94 w-m 22.56 3.94 w-m 23.40 3.80 m 22.75-23.2* 3.90-3.83 vs 23.06 3.85 vs 24.23 3.67 w-m 23.40 3.80 s 23.40 3.80 s25.22 3.53 m 24.17 3.68 m 24.12 3.69 m 29.08 3.07 w-m 24.92-25.37*3.57-3.51 m 25.06 3.55 m 45.36 2.00 w 28.71-29.27* 3.11-3.05 w-m 28.823.10 w-m 45.34 2.00 w 45.32 2.00 w *composite peak consisting ofmultiple overlapping reflections **Typically a shoulder

The zeolite may be yet further characterized by the x-ray diffractionpattern having at least the d-spacings and intensities set forth inTable B3 where the d-spacings and intensities are provided at differentrelative concentrations of the components of the coherently growncomposite structure.

TABLE B3 I II III high TUN, low IMF med TUN, med IMF low TUN, high IMF2-Theta d(†) I/Io % 2-Theta d(†) I/Io % 2-Theta d(†) I/Io % 7.12 12.40 w-m  7.11 12.42  w-m 7.16 12.25  vw-w 7.5-8.1* 11.78-10.91 m 7.5-8.1*11.78-10.91 m-s 7.5-8.1* 11.78-10.91 m-s 8.84 10.00  m-s  8.84 10.00 m-s 8.84 10.00  m-s 9.06 9.75 m  9.08 9.73 m  9.06** 9.75 w 9.24** 9.56vw-w  9.24 9.56 m 9.24 9.56 m 12.53 7.06 w 11.76 7.52 vw-w 11.76 7.52vw-w 14.38 6.15 w 12.48 7.09 m 12.46 7.10 m 14.64 6.05 vw 14.38 6.15vw-w 14.38 6.15 vw 15.26 5.80 vw-w 14.64 6.05 vw-w 14.64 6.05 w 15.525.70 vw 15.26 5.80 w 15.26 5.80 w 16.46 5.38 vw 15.52 5.70 w-m 15.525.70 w-m 17.72 5.00 w 16.50 5.37 vw-w 16.58 5.34 w 22.56** 3.94 vw-w17.72 5.00 w-m 17.72 5.00 w-m 22.89 3.88 vs 18.64 4.76 vw-w 18.64 4.76 w23.06** 3.85 w-m  22.56** 3.94 w-m 22.56 3.94 w-m 23.40 3.80 m22.75-23.2* 3.90-3.83 vs 23.06 3.85 vs 23.82 3.73 w-m 23.40 3.80 s 23.403.80 s 24.23 3.67 w-m 24.17 3.68 m 24.12 3.69 m 24.70 3.60 w-m 24.703.60 w-m 25.06 3.55 m 25.22 3.53 m 24.92-25.37* 3.57-3.51 m 26.16 3.40vw-w 26.51 3.36 w-m 26.32 3.38 w 26.74 3.33 w-m 29.08 3.07 w-m 26.763.33 w-m 28.82 3.10 w-m 35.86 2.50 vw-w 28.71-29.27* 3.11-3.05 w-m 30.122.96 w 45.36 2.00 w 30.13 2.96 vw-w 35.86 2.50 vw-w 45.66-47.37*1.98-1.91 vw-w 35.86 2.50 vw-w 45.32 2.00 w 45.34 2.00 w 45.66-47.37*1.98-1.91 vw-w 45.66-47.37* 1.98-1.91 vw-w *composite peak consisting ofmultiple overlapping reflections **Typically a shoulder

In Tables B2 and B3, the term “high” refers to about 60 to about 95mass-% of the specified component, the term “med” refers to about 25 toabout 70 mass-% of the specified component, and the term “low” refers toabout 5 to about 40 mass-% of the specified component. Some peaks may beshoulders on more intense peaks, and some peaks may be a composite peakconsisting of multiple overlapping reflections.

After acid treating, such as exposure to HNO₃ or H₂SiF₆, and on ananhydrous basis, the microporous crystalline zeolite UZM-39 has athree-dimensional framework of at least AlO₂ and SiO₂ tetrahedral unitsand an empirical composition in the acid treated form expressed by anempirical formula ofM1_(a) ^(N+)Al_((1-x))E_(x)Si_(y′)O_(z″)where M1 is at least one exchangeable cation selected from the groupconsisting of alkali, alkaline earth metals, rare earth metals, ammoniumion, hydrogen ion and combinations thereof, “a” is the mole ratio of M1to (Al+E) and varies from about 0.05 to about 50, “N” is the weightedaverage valence of M1 and has a value of about +1 to about +3, E is anelement selected from the group consisting of gallium, iron, boron, andcombinations thereof, x is the mole fraction of E and varies from 0 to1.0, y′ is the mole ratio of Si to (Al+E) and varies from greater thanabout 9 to virtually pure silica and z″ is the mole ratio of O to (Al+E)and has a value determined by the equation:z″=(a·N+3+4·y′)/2

Similar to the as-synthesized material, the modified UZM-39 materialsare thermally stable up to a temperature of at least 600° C. and inanother embodiment, up to at least 800° C. and may have a microporevolume as a percentage of total pore volume of greater than 60%.

By virtually pure silica is meant that virtually all the aluminum and/orthe E metals have been removed from the framework. It is well known thatit is virtually impossible to remove all the aluminum and/or E metal.Numerically, a zeolite is virtually pure silica when y′ has a value ofat least 3,000, preferably 10,000 and most preferably 20,000. Thus,ranges for y′ are from 9 to 3,000; from greater than 20 to about 3,000;from 9 to 10,000; from greater than 20 to about 10,000; from 9 to20,000; and from greater than 20 to about 20,000.

In specifying the proportions of the zeolite starting material oradsorption properties of the zeolite product and the like herein, the“anhydrous state” of the zeolite will be intended unless otherwisestated. The term “anhydrous state” is employed herein to refer to azeolite substantially devoid of both physically adsorbed and chemicallyadsorbed water.

The UZM-39 zeolite is employed as at least a portion of a catalyst in adehydrocyclodimerization process for preparing an aromatic stream from alight aliphatic hydrocarbon stream. The process uses adehydrocyclodimerization catalyst which comprises the UZM-39 zeolitecomponent, optionally a binder component, and optionally a metalcomponent. The metal component may be a metal such as gallium to promotethe dehydrogenation function. The gallium component may be incorporatedinto the catalytic composite in any suitable manner known to the artwhich results in a uniform dispersion of the gallium such as byion-exchange, cogelation, or impregnation either after, before, orduring the compositing of the catalyst formulation. Usually the galliumis deposited onto the catalyst by impregnating the catalyst with a saltof the gallium metal. The particles are impregnated with using galliummetal or gallium containing compounds such as gallium oxyhydroxide,gallium nitrate, gallium chloride, gallium bromide, gallium sulfate,gallium acetate, and gallium oxide. The amount of gallium which isdeposited onto the catalyst varies from about 0.1 to about 5 weightpercent of the finished catalyst expressed as the metal. The galliumcompound may be impregnated onto the support particles by any techniquewell known in the art such as dipping the catalyst into a solution ofthe metal compound or spraying the solution onto the support. One methodof preparation involves the use of a steam jacketed rotary dryer. Thesupport particles are immersed in the impregnating solution contained inthe dryer and the support particles are tumbled therein by the rotatingmotion of the dryer. Evaporation of the solution in contact with thetumbling support is expedited by applying steam to the dryer jacket.Following drying, the gallium impregnated catalyst may then be calcinedto convert the gallium to the oxide phase. An exemplary method forperforming the gallium incorporation step is disclosed in U.S. Pat. No.6,657,096, hereby incorporated by reference.

The zeolite as outlined above, or a modification thereof, may be in acomposite with commonly known binders. The UZM-39 is used as a catalystor catalyst support in various reactions. The UZM-39 preferably is mixedwith a binder for convenient formation of catalyst particles in aproportion of about 5 to 100 mass % UZM-39 zeolite and 0 to 95 mass-%binder, with the UZM-39 zeolite preferably comprising from about 10 to90 mass-% of the composite. The binder should preferably be porous, havea surface area of about 5 to about 800 m²/g, and be relativelyrefractory to the conditions utilized in the hydrocarbon conversionprocess. Non-limiting examples of binders are alumina, titania,zirconia, zinc oxide, magnesia, boria, silica-alumina, silica-magnesia,chromia-alumina, alumina-boria, aluminophosphates, silica-zirconia,silica, silica gel, and clays. Preferred binders are aluminophosphates,amorphous silica and alumina, including gamma-, eta-, and theta-alumina,with aluminophosphates being especially preferred.

The zeolite with or without a binder can be formed into various shapessuch as pills, pellets, extrudates, spheres, etc. Preferred shapes areextrudates and spheres. Extrudates are prepared by conventional meanswhich involves mixing of the composition either before or after addingmetallic components, with the binder and a suitable peptizing agent toform a homogeneous dough or thick paste having the correct moisturecontent to allow for the formation of extrudates with acceptableintegrity to withstand direct calcination. The dough then is extrudedthrough a die to give the shaped extrudate. A multitude of differentextrudate shapes are possible, including, but not limited to, cylinders,cloverleaf, dumbbell and symmetrical and asymmetrical polylobates. It isalso within the scope of this invention that the extrudates may befurther shaped to any desired form, such as spheres, by any means knownto the art.

Spheres can be prepared by the well known oil-drop method which isdescribed in U.S. Pat. No. 2,620,314 which is incorporated by reference.The method involves dropping a mixture of zeolite, and for example,alumina sol, and gelling agent into an oil bath maintained at elevatedtemperatures. The droplets of the mixture remain in the oil bath untilthey set and form hydrogel spheres. The spheres are then continuouslywithdrawn from the oil bath and typically subjected to specific agingtreatments in oil and an ammoniacal solution to further improve theirphysical characteristics. The resulting aged and gelled particles arethen washed and dried at a relatively low temperature of about 50 toabout 200° C. and subjected to a calcination procedure at a temperatureof about 450 to about 700° C. for a period of about 1 to about 20 hours.This treatment effects conversion of the hydrogel to the correspondingoxide or phosphate matrix.

The dehydrocyclodimerization conditions which are employed varydepending on such factors as feedstock composition and desiredconversion. A desired range of conditions for thedehydrocyclodimerization of C₂-C₆ aliphatic hydrocarbons to aromaticsinclude a temperature from about 350° C. to about 650° C. (662° F. to1202° F.), a pressure from about 0 to about 300 psi(g) (0 to 2068kPa(g)), and a liquid hourly space velocity from about 0.2 to about 5hr⁻¹. One embodiment of the invention employs process conditionsincluding a temperature in the range from about 400° C. to about 600° C.(752° F. to 1112° F.), a pressure in or about the range from about 0 toabout 150 psi(g) (0 to 1034 kPa(g)), and a liquid hourly space velocityof between 0.5 to 3.0 hr⁻¹. It is understood that, as the average carbonnumber of the feed increases, a temperature in the lower end of thetemperature range is required for optimum performance and conversely, asthe average carbon number of the feed decreases, the higher the requiredtemperature.

The feed stream to the dehydrocyclodimerization process is definedherein as all streams introduced into the dehydrocyclodimerizationreaction zone. Included in the feed stream is the at least one aliphatichydrocarbon having from 2 to about 6 carbon atoms. The feed stream isreferred to as comprising C₂-C₆ aliphatic hydrocarbons. By C₂-C₆aliphatic hydrocarbons is meant one or more open, straight or branchedchain isomers having from two to six carbon atoms per molecule.Furthermore, the hydrocarbons in the feedstock may be saturated orunsaturated. Preferably, the hydrocarbons are C₃'s and/or C₄'s selectedfrom isobutane, normal butane, isobutene, normal butene, propane andpropylene. Examples of potential feed streams include C₃ and/or C₄derived streams from FCC cracked products, light gasses from a delayedcoking process, and liquefied petroleum gas streams (LPG). Diluents mayalso be included in the feed stream. Examples of such diluents includewater, nitrogen, helium, argon, neon. Aromatic products generated by thedehydrocyclodimerization process may include benzene, toluene, xylenes,aromatics with 9 or 10 carbon atoms, and mixtures thereof. In oneembodiment, the aromatic products include benzene, toluene, and xylenes.The aromatic products may be used as reactants in later refining orpetrochemical processes.

Molecular hydrogen is produced in a dehydrocyclodimerization reaction aswell as aromatic hydrocarbons. For example, reacting a C₄ paraffin willyield 5 moles of hydrogen for every one mole of aromatic produced.Because the equilibrium concentration of aromatics is inverselyproportional to the fifth power of the hydrogen concentration, it isdesired to carry out the reaction in the absence of added hydrogen.Adherence to this practice, however, promotes catalyst deactivation and,as a result, short catalyst life before regeneration. The rapiddeactivation is believed to be caused by excessive carbon formation(coking) on the catalyst surface. This coking tendency makes itnecessary to relatively frequently perform catalyst regeneration.Reducing the deactivation occurring during successive regenerationsrequires a hydrothermally stable zeolite, that is, a zeolite for whichsurface area, micropore volume and/or tetrahedral Al content are stableafter exposure to high temperatures and steam quantities. The catalystused in this dehydrocyclodimerization has the advantage of hydrothermalstability which may lead to longer catalyst life.

The catalyst may be in a fixed bed system, a moving bed system, afluidized bed system, or in a batch type operation; however, in view ofthe danger of attrition losses of the valuable catalyst and of thewell-known operational advantages, it is preferred to use either a fixedbed system or a dense-phase moving bed system.

In a fixed bed system or a dense-phase moving bed system, the feedstream is preheated by any suitable heating means to the desiredreaction temperature and then passed into a dehydrocyclodimerizationzone containing a bed of catalyst. It is understood that thedehydrocyclodimerization zone may be one or more separate reactors withsuitable means between separate reactors if any to compensate for anyendothermicity encountered in each reactor and to assure that thedesired temperature is maintained at the entrance to each reactor. It isalso important to note that the feed stream may be contacted with thecatalyst bed in either upward, downward, or radial flow fashion with thelatter being preferred. In addition, the feed stream is in the vaporphase when its' components contact the catalyst bed. Each reactor maycontain one or more fixed or dense-phase moving beds of catalyst.

The dehydrocyclodimerization system may comprise adehydrocyclodimerization zone containing one or more reactors and/orbeds of catalyst. In a multiple bed system, it is, of course, within thescope of the present invention to use one catalyst in less than all ofthe beds with another dehydrocyclodimerization or similarly behavingcatalyst being used in the remainder of the beds. Specific to thedense-phase moving bed system, it is common practice to remove catalystfrom the bottom of a reactor in the dehydrocyclodimerization zone,regenerate it by conventional means known to the art, and then return itto the top of that reactor or another reactor in thedehydrocyclodimerization zone. The reactor or reactors utilized in theprocess may be linked to a product recovery system in various mannersdescribed in the prior art to achieve specific desired results. U.S.Pat. No. 4,642,402 for example discloses a method of combining areaction zone and product recovery zone to optimize the xylene producedin a dehydrocyclodimerization process. The product recovery section mayrecover streams such as hydrogen, light hydrocarbons, and benzene. In anembodiment, at least a portion of a light hydrocarbon stream comprisingC₂-C₆ hydrocarbons is recycled to the dehydrocyclodimerization zone as aportion of the feedstream. In another an embodiment, at least a portionof the benzene stream is recycled to the dehydrocyclodimerization zoneas a portion of the feedstream

After some time on stream (several days to a year), the catalystdescribed above will have lost enough activity due to coking andhydrogen exposure so that it must be reactivated. It is believed thatthe exact amount of time which a catalyst can operate withoutnecessitating regeneration or reactivation will depend on a number offactors. One factor, as is demonstrated herein is whether water is addedto the feed stream.

When the catalyst requires regeneration, typically oxidation or burningof catalyst deactivating carbonaceous deposits with oxygen or anoxygen-containing gas is used. Catalyst regeneration techniques are wellknown and not discussed in detail here. Examples include U.S. Pat. No.4,795,845 (hereby incorporated by reference) which discloses burning thecoke accumulated upon the deactivated catalyst at catalyst regenerationconditions in the presence of an oxygen-containing gas, and U.S. Pat.No. 4,724,271 (hereby incorporated by reference) which additionallydiscloses water removal steps in the catalyst regeneration procedure.The regeneration may proceed in one or multiple burns. For example,there may be a main burn followed by a clean-up burn. The main burnconstitutes the principal portion of the regeneration process with theclean-up burn gradually increasing the amount of molecular oxygen in thegas introduced to the regeneration catalyst until the end of theclean-up burn which is indicated by a gradual decline in the temperatureat the edit of the catalyst bed until the inlet and outlet temperaturesof the catalyst bed merges.

In addition to deactivation by coking requiring regeneration,dehydrocyclodimerization catalysts can be deactivated by exposure tohydrogen at high temperatures and then require reactivation. Similarly,when the catalyst requires reactivation, it is removed from theoperating reactor and contacted with fluid water. Suitable reactivationprocesses are known and not discussed in detail here. One example isU.S. Pat. No. 6,395,664. Using procedures in the art, the catalyst canbe reactivated multiple times. Thus, the catalyst can be hydrogendeactivated, then reactivated, then hydrogen deactivated again, thenreactivated again and so forth. No limit on the number of times that aparticular catalyst can be deactivated and subsequently reactivated isknown. The application and use of additional required items are wellwithin the purview of a person of ordinary skill in the art. U.S. Pat.No. 3,652,231; U.S. Pat. No. 3,647,680; and U.S. Pat. No. 3,692,496;which are incorporated by reference into this document, may be consultedfor additional detailed information.

The following examples are presented in illustration of this inventionand are not intended as undue limitations on the generally broad scopeof the invention as set out in the appended claims.

The structure of the UZM-39 zeolite of this invention was determined byx-ray analysis. The x-ray patterns presented in the following exampleswere obtained using standard x-ray powder diffraction techniques. Theradiation source was a high-intensity, x-ray tube operated at 45 kV and35 ma. The diffraction pattern from the copper K-alpha radiation wasobtained by appropriate computer based techniques. Flat compressedpowder samples were continuously scanned at 2° to 56° (2θ). Interplanarspacings (d) in Angstrom units were obtained from the position of thediffraction peaks expressed as 0 where 0 is the Bragg angle as observedfrom digitized data. Intensities were determined from the integratedarea of diffraction peaks after subtracting background, “I_(o)” beingthe intensity of the strongest line or peak, and “I” being the intensityof each of the other peaks.

As will be understood by those skilled in the art the determination ofthe parameter 2θ is subject to both human and mechanical error, which incombination can impose an uncertainty of about ±0.4° on each reportedvalue of 2θ. This uncertainty is, of course, also manifested in thereported values of the d-spacings, which are calculated from the 2θvalues. This imprecision is general throughout the art and is notsufficient to preclude the differentiation of the present crystallinematerials from each other and from the compositions of the prior art. Insome of the x-ray patterns reported, the relative intensities of thed-spacings are indicated by the notations vs, s, m, and w whichrepresent very strong, strong, medium, and weak, respectively. In termsof 100×I/I_(o), the above designations are defined as:vw=<5;w=6-15;m=16-50:s=51-80; and vs=80-100

In certain instances the purity of a synthesized product may be assessedwith reference to its x-ray powder diffraction pattern. Thus, forexample, if a sample is stated to be pure, it is intended only that thex-ray pattern of the sample is free of lines attributable to crystallineimpurities, not that there are no amorphous materials present.

In order to more fully illustrate the invention, the following examplesare set forth. It is to be understood that the examples are only by wayof illustration and are not intended as an undue limitation on the broadscope of the invention as set forth in the appended claims.

EXAMPLE 1

A sample of UZM-39 was prepared as follows. 6.02 g of NaOH, (97%) wasdissolved in 125.49 g water. 0.62 g Al(OH)₃, (29.32 wt.-% Al) was addedto the NaOH solution to form a first solution. Separately, 0.24 g of thelayered material UZM-8 was stirred into 30.0 g Ludox AS-40 to form asecond solution. The second solution was added to the first solution.The mixture was cooled to 0° C.-4° C. Separately, 6.54 g1,4-dibromobutane, (99 wt.-%) was mixed with 7.65 g 1-methylpyrrolidine,(97 wt.-%) to form a third solution. The third solution was added to thecooled mixture of the first and second solutions to form the finalreaction mixture. The final reaction mixture was transferred to a 300 ccstirred autoclave and digested at 160° C. for 144 hours with stirring at100 rpm. The product was isolated by filtration. The product wasidentified as UZM-39 by XRD as shown in FIG. 1. Analytical results showthis material has the following molar rations: Si/Al of 12.64, Na/Al of0.116, N/Al of 0.92, C/N of 7.23.

Scanning Electron Microscopy (SEM) revealed crystals of intergrown,square rod morphology in starbursts, approximately 250 to 700 nm along aface of the square with an aspect ratio of from 2:1 to 5:1. Themicrograph is shown in FIG. 7. The product was calcined at 550° C. for 3hrs under air. The XRD pattern of the calcined material is shown in FIG.2.

COMPARATIVE EXAMPLE 2

The preparation of Example 1 was followed, except that the layeredmaterial UZM-8 was not added to the second solution. After 144 hours ofstirring at 100 rpm at 160° C., the product was isolated by filtration.The product was identified as analcime by XRD.

COMPARATIVE EXAMPLE 3

6.68 g of NaOH, (97%) was dissolved in 145.44 g water. 2.86 gAl(NO₃)₃.9H₂O (97%) was added to the sodium hydroxide solution. 13.33 gAerosil 200 was stirred into the mixture. 13.1 g H₂O was added. 7.26 g1,4-dibromobutane, (99%) and 5.84 g 1-methylpyrrolidine, (97%) wereadded and the mixture was stirred vigorously for a day. The mixture wasdivided equally and loaded into eight 45 cc Parr vessels and placed intoa rotisserie oven at 160°. The mixture in one of the Parr vesselsproduced a material at 256 hours identified by XRD as having the TUNstructure. Analytical results showed this material to have the followingmolar ratios, Si/Al of 15.51, Na/Al of 0.12, N/Al of 1.29, and C/N of6.89. SEM analysis revealed a squat rod cluster morphology, about300-800 nm in length and with an aspect ratio of about 1.

The product generated by this synthesis was calcined under flowing airat 600° for 6 hours. It was then ion exchanged four times with 1 Mammonium nitrate solution at 75° followed by a calcination at 500° underair for 2 hours to convert NH₄ ⁺ into H. Analysis for the calcined,ion-exchanged sample showed 39.2 wt. % Si, 2.34 wt. % Al, <0.005 wt. %Na with a BET surface area of 378 m²/g, pore volume of 0.220 cm³/g, andmicropore volume of 0.190 cm³/g.

Analysis of the H+-form of this material by Rietveld XRD refinementshowed that the material consisted entirely of TUN structure type. TEManalysis confirmed that no coherent growth of IMF crystals occurred.

EXAMPLE 4

6.40 g of NaOH, (97%) was dissolved in 111.88 g water. 1.16 g Al(OH)₃,(29.32 wt.-% Al), was added to the sodium hydroxide solution to create afirst solution. Separately, 0.30 g of the layered material (UZM-8) wasstirred into 37.5 g Ludox AS-40 to form a second solution. The secondsolution was added to the first solution and vigorously stirred for 1-2hours. The mixture was cooled to 0° C.-4° C. Separately, 8.18 g1,4-dibromobutane, (99 wt.-%) was mixed with 9.56 g 1-methylpyrrolidine,(97 wt.-%) to form a third solution. The third solution was added to thecooled mixture to create the final reaction mixture. The final reactionmixture was vigorously stirred and transferred to a 300 cc stirredautoclave. The final reaction mixture was digested at 160° C. for 144hours with stirring at 100 rpm. The product was isolated by filtration.The product was identified as UZM-39 by XRD. Analytical results showedthis material to have the following molar ratios, Si/Al of 12.07, Na/Alof 0.124, N/Al of 0.90, C/N of 6.85.

EXAMPLE 5

7.19 g of NaOH, (99 wt.-%%) was dissolved in 90.1 g water. 1.56 gAl(OH)₃, (29.32 wt.-% Al), was added to the sodium hydroxide solution tocreate a first solution. Separately, 0.405 g of the layered material(UZM-8) was stirred into 50.62 g Ludox AS-40 to form a second solution.The second solution was added to the first solution and vigorouslystirred for 1-2 hours. The mixture was cooled to 0° C.-4° C. Separately,11.04 g 1,4-dibromobutane, (99 wt.-%), was mixed with 12.90 g1-methylpyrrolidine, (97 wt.-%) to form a third solution. The thirdsolution was added to the cooled mixture to create the final reactionmixture. The final reaction mixture was vigorously stirred for 5 minutesand transferred to a 300 cc stirred autoclave. The final reactionmixture was digested at 160° C. for 144 hours with stirring at 100 rpm.16.5 g of the product was isolated by filtration. The product wasidentified by XRD to be UZM-39 with a very slight MOR impurity.Analytical results showed this material to have the following molarratios, Si/Al of 14.14, Na/Al of 0.16, N/Al of 1.02, C/N of 7.33.

EXAMPLE 6

37.62 g of NaOH, (97 wt.-%) was dissolved in 600 g water to create asodium hydroxide solution. 6.96 g Al(OH)₃ (29.32 mass % Al) was added tothe sodium hydroxide solution to create a first solution. Separately,1.80 g of the layered material (UZM-8) was stirred into 225 g LudoxAS-40 to form a second solution. The second solution was added to thefirst solution and vigorously stirred for 1-2 hours. The mixture wascooled to 0° C.-4° C. Separately, 49.08 g 1,4-dibromobutane (99 wt.-%)was mixed with 57.36 g 1-methylpyrrolidine (97 wt.-%) for 1-5 minutes toform a third solution. The third solution was added to the cooledmixture to create the final reaction mixture. The final reaction mixturewas vigorously stirred for 5 minutes and transferred to a 2 literstirred autoclave. The final reaction mixture was digested at 160° C.for 144 hours with stirring at 250 rpm. The product was isolated byfiltration. The product was identified by XRD as UZM-39. Analyticalresults showed this material to have the following molar ratios, Si/Alof 11.62, Na/Al of 0.12, N/Al of 0.88, C/N of 7.36.

The product generated by this synthesis was calcined under flowing airat 600° for 6 hours. It was then ion exchanged four times with 1 Mammonium nitrate solution at 75° followed by a calcination at 500° C.under air for 2 hours to convert NH₄ ⁺ into H⁺. Analysis of the H⁺ formof this material by Rietveld XRD refinement gave the results shown inTable 1.

EXAMPLE 7

505.68 g of NaOH, (99 wt.-%) was dissolved in 10542 g water. 52.08 gAl(OH)₃, (29.3 wt.-% Al), was added to the sodium hydroxide solution tocreate a first solution. Separately, 20.16 g of the layered material(UZM-8) was stirred into 2520 g Ludox AS-40 to form a second solution.The second solution was added to the first solution and vigorouslystirred for 1-2 hours. The mixture was cooled to 0° C.-4° C. Separately,549.36 g 1,4-dibromobutane (99 wt.-%) was mixed with 642.6 g1-methylpyrrolidine, (97 wt.-%), for 3-5 minutes to form a thirdsolution. The third solution was added to the cooled mixture to createthe final reaction mixture. The final reaction mixture was vigorouslystirred for 5 minutes and pumped into a 5 gallon stirred autoclave. Thefinal reaction mixture was digested at 160° C. for 150 hours withstirring at 100 rpm. The product was isolated by filtration. The productwas identified by XRD as UZM-39. Analytical results showed this materialto have the following molar ratios, Si/Al=13.35, Na/Al=0.087, N/Al=0.96,C/N=7.12.

EXAMPLE 8

The preparation of Example 4 was followed except that UZM-8 was replacedwith 0.30 g UZM-26. The product was identified by XRD as UZM-39.Analytical results showed this material to have the following molarratios: Si/Al=12.88, Na/Al=0.25, N/Al=0.88, C/N=7.31.

EXAMPLE 9

6.27 g of NaOH, (99%), was dissolved in 111.88 g water to create asodium hydroxide solution. 1.16 g Al(OH)₃ (29.32 mass % Al) was added tothe sodium hydroxide solution to create a first solution. 37.5 g LudoxAS-40 and then 0.22 g of the layered material UZM-5 were added to thefirst solution. The first solution was vigorously stirred for 1-2 hours.The first solution was cooled to 0° C.-4° C. Separately, 8.18 g1,4-dibromobutane (99%) was mixed with 9.56 g 1-methylpyrrolidine (97%)for 1-5 minutes to form a second solution. The second solution was addedto the cooled first solution to create the final reaction mixture. Thefinal reaction mixture was vigorously stirred for approximately 5minutes and transferred to a 300 cc stirred autoclave. The finalreaction mixture was digested at 160° C. for 144 hours with stirring at100 rpm. The product was isolated by filtration. The product wasidentified by XRD as UZM-39 with a very small EUO or NES contaminant.

COMPARATIVE EXAMPLE 10

This example is identical to example 4 except that UZM-8 was replacedwith 0.30 g UZM-39. The product was identified as a compositioncomprising MTW, UZM-39, ANA and MOR.

EXAMPLE 11

6.27 g of NaOH, (97 wt.-%) was dissolved in 111.88 g water. 1.16 gAl(OH)₃, (29.32 wt. % Al), was added to the sodium hydroxide solution tocreate a first solution. Separately, 0.30 g of the layered material(UZM-8) was stirred into 37.5 g Ludox AS-40 to form a second solution.The second solution was added to the first solution and vigorouslystirred for 1-2 hours. The mixture was cooled to 0° C.-4° C. Separately,12.27 g 1,4-dibromobutane (99 wt.-%) was mixed with 14.34 g1-methylpyrrolidine (97 wt.-%) to form a third solution. The thirdsolution was added to the cooled mixture to create the final reactionmixture. The final reaction mixture was vigorously stirred andtransferred to a 300 cc stirred autoclave. The final reaction mixturewas digested at 160° C. for 144 hours with stirring at 100 rpm. Theproduct was isolated by filtration. The product was identified as UZM-39with an ESV impurity by XRD. Analytical results showed this material tohave the following molar ratios, Si/Al=13.17, Na/Al=0.126, N/Al=1.03,C/N=7.22.

EXAMPLE 12

The procedure of Example 4 was followed except 9.56 g1-methylpyrrolidine, (97 wt.-%), was replaced with 8.05 gdimethylethylamine, (97 wt.-%). The product was identified as acomposition comprising mordenite and UZM-39.

EXAMPLE 13

6.27 g of NaOH (99 wt.-%) was dissolved in 111.88 g water. 1.16 gAl(OH)₃ (29.32 wt.-% Al) was added to the sodium hydroxide solution tocreate a first solution. 0.30 g of the layered material UZM-8 and 37.5 gLudox AS-40 were added to the first solution. The first solution wasvigorously stirred for 1-2 hours. The first solution was cooled to 0°C.-4° C. Separately, 4.02 g dimethylethylamine (97 wt.-%) was mixed with4.78 g 1-methylpyrrolidine (97 wt.-%) for 1-2 minutes to form an aminesolution. 8.18 g 1,4-dibromobutane (99 wt.-%) was added to the aminesolution and then mixed for 1-2 minutes to form a second solution. Thesecond solution was added to the cooled first solution to create thefinal reaction mixture. The final reaction mixture was vigorouslystirred for approximately 5 minutes and transferred to a 300 cc stirredautoclave. The final reaction mixture was digested at 160° C. for 192hours with stirring at 100 rpm. The product was isolated by filtration.The product was identified as UZM-39 by XRD. Analytical results showedthis material to have the following molar ratios, Si/Al=12.42,Na/Al=0.175, N/Al=0.91, C/N=6.92.

The product generated by this synthesis was calcined under flowing airat 600° for 6 hours. It was then ion exchanged four times with 1 Mammonium nitrate solution at 75° followed by a calcination at 500° C.under air for 2 hours to convert NH₄ ⁺ into H⁺. Analysis for thecalcined, ion-exchanged sample shows 38.7% Si, 2.97% Al, 0.0089% Na witha BET surface area of 375 m²/g, pore volume of 0.238 cm³/g, andmicropore volume of 0.184 cm³/g. Analysis of the H⁺ form of thismaterial by Rietveld XRD refinement gave the results shown in Table 1.

EXAMPLE 14

6.21 g of NaOH, (99%), was dissolved in 111.88 g water to create asodium hydroxide solution. 1.16 g Al(OH)₃ (29.32 wt.-% Al) was added tothe sodium hydroxide solution to create a first solution. 0.30 g of thelayered material (UZM-8) and 37.5 g Ludox AS-40 were added to the firstsolution. The first solution was vigorously stirred for 1-2 hours. Thefirst solution was cooled to 0° C.-4° C. Separately, 8.18 g1,4-dibromobutane (99 wt.-%) was mixed with 9.56 g 1-methylpyrrolidine(97 wt.-%) for 1-5 minutes to form a second solution. The secondsolution was added to the cooled first solution to create the finalreaction mixture. The final reaction mixture was vigorously stirred forapproximately 5 minutes and transferred to a 300 cc stirred autoclave.The final reaction mixture was digested at 170° C. for 96 hours withstirring at 100 rpm. The product was isolated by filtration. The productwas identified as UZM-39 by XRD. Analytical results showed this materialto have the following molar ratios, Si/Al of 12.76, Na/Al of 0.116, N/Alof 0.94, C/N of 6.98.

EXAMPLE 15

6.21 g of NaOH, (99%), was dissolved in 111.88 g water to create asodium hydroxide solution. 1.16 g Al(OH)₃ (29.32 wt.-% Al) was added tothe sodium hydroxide solution to create a first solution. 0.30 g of thelayered material (UZM-8) and 37.5 g Ludox AS-40 were added to the firstsolution. The first solution was vigorously stirred for 1-2 hours. Thefirst solution was cooled to 0° C.-4° C. Separately, 8.18 g1,4-dibromobutane (99 wt.-%) was mixed with 9.56 g 1-methylpyrrolidine(97 wt.-%) for 1-5 minutes to form a second solution. The secondsolution was added to the cooled first solution to create the finalreaction mixture. The final reaction mixture was vigorously stirred forapproximately 5 minutes and transferred to a 300 cc stirred autoclave.The final reaction mixture was digested at 175° C. for 44 hours withstirring at 100 rpm. The product was isolated by filtration. The productwas identified as UZM-39 by XRD. Analytical results showed this materialto have the following molar ratios, Si/Al of 12.97, Na/Al of 0.20, N/Alof 0.95, C/N of 6.98.

EXAMPLE 16

5.96 g of NaOH, (97%) and 0.25 g KOH, (86%) were dissolved in 111.88 gwater. 1.22 g Al(OH)₃, (27.9 wt.-% Al), was added to the sodiumhydroxide solution. 37.5 g Ludox AS-40 and then 0.30 g of the layeredmaterial UZM-8 were added to the first solution and stirred vigorouslyfor 1-2 hours. The mixture was cooled to 0° C.-4° C. Separately, 8.18 g1,4-dibromobutane, (99%) was mixed with 9.56 g 1-methylpyrrolidine,(97%) to form a third mixture. The third mixture was added to the cooledmixture to create the final reaction mixture. The final reaction mixturewas vigorously stirred and transferred to a 300 cc stirred autoclave.The final reaction mixture was digested at 160° C. for 144 hours withstirring at 100 rpm. The product was isolated by filtration. The productwas identified as UZM-39 by XRD. The x-ray diffraction pattern is shownin FIG. 3. Analytical results showed this material to have the followingmolar ratios, Si/Al of 11.69, Na/Al of 0.137, K/Al of 0.024, N/Al of0.848, C/N of 7.16.

The product generated by this synthesis was calcined under flowing airat 600° for 6 hours. It was then ion exchanged four times with 1 Mammonium nitrate solution at 75° followed by a calcination at 500° C.under air for 2 hours to convert NH₄ ⁺ into Ft. Analysis for thecalcined, ion-exchanged sample shows 39.4% Si, 3.23% Al, 0.011% Na,0.005% K with a BET surface area of 362 m²/g, pore volume of 0.231cm³/g, and micropore volume of 0.176 cm³/g. The x-ray diffractionpattern in shown in FIG. 4.

EXAMPLE 17

5.96 g of NaOH, (99%) and 0.50 g KOH, (86%) were dissolved in 111.88 gwater. 1.16 g Al(OH)₃, (29.32 wt.-% Al), was added to the sodiumhydroxide solution. 37.5 g Ludox AS-40 and then 0.30 g of the layeredmaterial UZM-8 were added to the first solution and stirred vigorouslyfor 1-2 hours. The mixture was cooled to 0° C.-4° C. Separately, 4.09 g1,4-dibromobutane, (99%) was mixed with 11.15 g 1-methylpyrrolidine,(97%) to form a third mixture. The third mixture was added to the cooledmixture to create the final reaction mixture. The final reaction mixturewas vigorously stirred and transferred to a 300 cc stirred autoclave.The final reaction mixture was digested at 160° C. for 144 hours withstirring at 100 rpm. The product was isolated by filtration. The productwas identified as UZM-39 by XRD. Analytical results showed this materialto have the following molar ratios, Si/Al of 11.98, Na/Al of 0.114, K/Alof 0.0375 N/Al of 0.84, C/N of 7.50.

The product generated by this synthesis was calcined under flowing airat 600° for 6 hours. It was then ion exchanged four times with 1 Mammonium nitrate solution at 75° followed by a calcination at 500° C.under air for 2 hours to convert NH₄ ⁺ into Ft. Analysis for thecalcined, ion-exchanged sample shows 37.7% Si, 3.01% Al, 0.012% Na,0.006% K. Analysis of the H⁺ form of this material by Rietveld XRDrefinement gave the results shown in Table 1. TEM analysis showed thatUZM-39 is a coherently grown composite structure of TUN and IMFzeotypes, the results of which analysis are shown in FIGS. 10 and 11.

EXAMPLE 18

5.64 g of NaOH, (97%) and 1.00 g KOH, (86%) were dissolved in 111.88 gwater. 1.22 g Al(OH)₃, (27.9 wt.-% Al), was added to the sodiumhydroxide solution. 37.5 g Ludox AS-40 and then 0.30 g of the layeredmaterial UZM-8 were added to the first solution and stirred vigorouslyfor 1-2 hours. The mixture was cooled to 0° C.-4° C. Separately, 8.18 g1,4-dibromobutane, (99%) was mixed with 9.56 g 1-methylpyrrolidine,(97%) to form a third mixture. The third mixture was added to the cooledmixture to create the final reaction mixture. The final reaction mixturewas vigorously stirred and transferred to a 300 cc stirred autoclave.The final reaction mixture was digested at 160° C. for 144 hours withstirring at 100 rpm. The product was isolated by filtration. The productwas identified as UZM-39 by XRD. Analytical results showed this materialto have the following molar ratios, Si/Al of 11.29, Na/Al of 0.078, K/Alof 0.053 N/Al of 0.88, C/N of 6.92. The SEM image of the product isshown in FIG. 8.

The product generated by this synthesis was calcined under flowing airat 600° for 6 hours. It was then ion exchanged four times with 1 Mammonium nitrate solution at 75° followed by a calcination at 500° C.under air for 2 hours to convert NH₄ ⁺ into Ft. Analysis for thecalcined, ion-exchanged sample shows 41.5% Si, 2.65% Al, 0.0018% Na,0.02% K with a BET surface area of 351 m²/g, pore volume of 0.218 cm³/g,and micropore volume of 0.170 cm³/g. Analysis of the H⁺ form of thismaterial by Rietveld XRD refinement gave the results shown in Table 1.

EXAMPLE 19

5.02 g of NaOH, (97%) and 2.00 g KOH, (86%) were dissolved in 111.88 gwater. 1.22 g Al(OH)₃, (27.9 wt.-% Al), was added to the sodiumhydroxide solution. 37.5 g Ludox AS-40 and then 0.30 g of the layeredmaterial UZM-8 were added to the first solution and stirred vigorouslyfor 1-2 hours. The mixture was cooled to 0° C.-4° C. Separately, 8.18 g1,4-dibromobutane, (99%) was mixed with 9.56 g 1-methylpyrrolidine,(97%) to form a third mixture. The third mixture was added to the cooledmixture to create the final reaction mixture. The final reaction mixturewas vigorously stirred and transferred to a 300 cc stirred autoclave.The final reaction mixture was digested at 160° C. for 136 hours withstirring at 100 rpm. The product was isolated by filtration. The productwas identified as UZM-39 by XRD with a likely small amount of NEScontaminant Analytical results showed this material to have thefollowing molar ratios, Si/Al of 10.99, Na/Al of 0.088, K/Al of 0.11N/Al of 0.84, C/N of 7.36.

EXAMPLE 20

5.96 g of NaOH, (99%) was dissolved in 111.88 g water. 1.22 g Al(OH)₃,(27.9 wt.-% Al), was added to the sodium hydroxide solution. Then 0.24 gMg(OH)₂ (95%), 37.5 g Ludox AS-40, and 0.30 g of the layered materialUZM-8 were added in the order listed to the first solution and stirredvigorously for 1-2 hours. The mixture was cooled to 0° C.-4° C.Separately, 8.18 g 1,4-dibromobutane, (99%) was mixed with 9.56 g1-methylpyrrolidine, (97%) and added to the cooled mixture to create thefinal reaction mixture. The final reaction mixture was vigorouslystirred and transferred to a 300 cc stirred autoclave. The finalreaction mixture was digested at 160° C. for 144 hours with stirring at100 rpm. The product was isolated by filtration. The product wasidentified as UZM-39 by XRD. Analytical results showed this material tohave the following molar ratios, Si/Al of 12.12, Na/Al of 0.148, Mg/Alof 0.38 N/Al of 0.91, C/N of 6.96.

The product generated by this synthesis was calcined under flowing airat 600° for 6 hours. It was then ion exchanged four times with 1 Mammonium nitrate solution at 75° followed by a calcination at 500° C.under air for 2 hours to convert NH₄ ⁺ into H⁺. Analysis for thecalcined, ion-exchanged sample shows 39.6% Si, 2.99% Al, 83 ppm Na,0.14% Mg with a BET surface area of 351 m²/g, pore volume of 0.218cm³/g, and micropore volume of 0.170 cm³/g.

EXAMPLE 21

5.96 g of NaOH, (99%) and 0.51 g La(OH)₃, (99.9%) were dissolved in111.88 g water. 1.16 g Al(OH)₃, (29.32 wt.-% Al), was added to thesodium hydroxide solution. 37.5 g Ludox AS-40 and then 0.30 g of thelayered material UZM-8 were added to the first solution and stirredvigorously for 1-2 hours. The mixture was cooled to 0° C.-4° C.Separately, 8.18 g 1,4-dibromobutane, (99%) was mixed with 9.56 g1-methylpyrrolidine, (97%) and added to the cooled mixture to create thefinal reaction mixture. The final reaction mixture was vigorouslystirred and transferred to a 300 cc stirred autoclave. The finalreaction mixture was digested at 160° C. for 168 hours with stirring at100 rpm. The product was isolated by filtration. The product wasidentified as UZM-39 by XRD. Analytical results showed this material tohave the following molar ratios, Si/Al of 12.22, Na/Al of 0.20, La/Al of0.18, N/Al of 0.89, C/N of 7.13.

The product generated by this synthesis was calcined under flowing airat 600° for 6 hours. It was then ion exchanged four times with 1 Mammonium nitrate solution at 75° followed by a calcination at 500° C.under air for 2 hours to convert NH₄ ⁺ into H⁺. Analysis for thecalcined, ion-exchanged sample shows 39.1% Si, 3.06% Al, 60 ppm Na,0.25% La with a BET surface area of 335 m²/g, pore volume of 0.226cm³/g, and micropore volume of 0.163 cm³/g.

EXAMPLE 22

3.14 g of NaOH, (97%) was dissolved in 106.41 g water. 1.16 g Al(OH)₃,(29.32 wt.-% Al), was added to the sodium hydroxide solution. 37.5 gLudox AS-40 and then 0.30 g of the layered material UZM-8 were added tothe first solution. Next 26.7 g Na silicate solution (13.2 wt. % Si;6.76 wt. % Na) is added to the above and stirred vigorously for 1-2hours. The mixture was cooled to 0° C.-4° C. Separately, 8.18 g1,4-dibromobutane, (99%) was mixed with 9.56 g 1-methylpyrrolidine,(97%) to form a third mixture. The third mixture was added to the cooledmixture to create the final reaction mixture. The final reaction mixturewas vigorously stirred and transferred to a 300 cc stirred autoclave.The final reaction mixture was digested at 160° C. for 224 hours withstirring at 100 rpm. The product was isolated by filtration. The productwas identified as UZM-39 by XRD. Analytical results showed this materialto have the following molar ratios, Si/Al of 11.75, Na/Al of 0.11, N/Alof 0.90, C/N of 6.99.

The product generated by this synthesis was calcined under flowing airat 600° for 6 hours. It was then ion exchanged three times with 1 Mammonium nitrate solution at 75° followed by a calcination at 500° C.under air for 2 hours to convert NH₄ ⁺ into H⁺. Analysis for thecalcined, ion-exchanged sample shows 38.8% Si, 3.05% Al, 0.011% Na, witha BET surface area of 364 m²/g, pore volume of 0.273 cm³/g, andmicropore volume of 0.174 cm³/g. Analysis of the H⁺ form of thismaterial by Rietveld XRD refinement gave the results shown in Table 1.

EXAMPLE 23

5.33 g of NaOH, (99%) was dissolved in 111.88 g water. 1.16 g Al(OH)₃,(29.32 wt.-% Al), was added to the sodium hydroxide solution.Separately, 0.30 g of Beta zeolite was stirred into 37.5 g Ludox AS-40to make a second mixture. This second mixture was added to the firstsolution and stirred vigorously for 1-2 hours. The mixture was cooled to0° C.-4° C. Separately, 8.89 g 1,5-dibromopentane, (97%) was mixed with9.56 g 1-methylpyrrolidine, (97%) to form a third mixture. The thirdmixture was added to the cooled mixture to create the final reactionmixture. The final reaction mixture was vigorously stirred andtransferred to a 300 cc stirred autoclave. The final reaction mixturewas digested at 160° C. for 256 hours with stirring at 100 rpm. Theproduct was isolated by filtration. The product was identified as UZM-39by XRD. Analytical results showed this material to have the followingmolar ratios, Si/Al of 13.24, Na/Al of 0.13, N/Al of 0.91, C/N of 7.21.

The product generated by this synthesis was calcined under flowing airat 600° for 6 hours. It was then ion exchanged three times with 1 Mammonium nitrate solution at 75° followed by a calcination at 500° C.under air for 2 hours to convert NH₄ ⁺ into H⁺. Analysis of the H⁺ formof this material by Rietveld XRD refinement gave the results shown inTable 1.

COMPARATIVE EXAMPLE 24

10.8 g of Aerosil 200 was added, while stirring, to a solution of 12.24g 1,5-bis(N-methylpyrrolidinium)pentane dibromide in 114 g H₂O. A verythick gel was formed. Separately, a solution was made from 60 g H₂O,3.69 g NaOH (99%), 0.95 g sodium aluminate (26.1% Al by analysis), and1.86 g NaBr (99%). This second solution was added to the above mixturewhich thins out a bit. The final mixture was divided equally between 745 cc Parr vessels. One vessel, which was digested for 12 days at 170°C. in a rotisserie oven at 15 rpm, yielded a product which wasdetermined by XRD as having the IMF structure. The product was isolatedby filtration. The product generated by this synthesis was calcinedunder flowing air at 600° for 6 hours. It was then ion exchanged fourtimes with 1 M ammonium nitrate solution at 75° followed by acalcination at 500° under air for 2 hours to convert NH₄ ⁺ into Ft.Analysis of the H+-form of this material by Rietveld XRD refinementshowed that the material consisted entirely of IMF structure type. TEManalysis confirmed that no coherent growth of TUN crystals occurred.

EXAMPLE 25

31.98 g of NaOH, (99%) was dissolved in 671.3 g water. 6.96 g Al(OH)₃,(29.32 wt.-% Al), was added to the sodium hydroxide solution.Separately, 1.80 g of the layered material UZM-8 was stirred into 225.0g Ludox AS-40 to make a second mixture. This second mixture was added tothe first solution and stirred vigorously for 1-2 hours. The mixture wascooled to 0° C.-4° C. Separately, 53.34 g 1,5-dibromopentane, (97%) wasmixed with 57.36 g 1-methylpyrrolidine, (97%) to form a third mixture.The third mixture was added to the cooled mixture to create the finalreaction mixture. The final reaction mixture was vigorously stirred andtransferred to a 2 L stirred autoclave. The final reaction mixture wasdigested at 160° C. for 256 hours with stirring at 250 rpm. The productwas isolated by filtration. The product was identified as UZM-39 by XRD.Analytical results showed this material to have the following molarratios, Si/Al of 12.30, Na/Al of 0.13, N/Al of 0.92, C/N of 7.51.

The product generated by this synthesis was calcined under flowing airat 600° for 6 hours. It was then ion exchanged three times with 1 Mammonium nitrate solution at 75° followed by a calcination at 500° underair for 2 hours to convert NH₄ ⁺ into H. Analysis for the calcined,ion-exchanged sample shows 39.0% Si, 2.93% Al, 0.008% Na. Analysis ofthe H+-form of this material by Rietveld XRD refinement gave the resultsshown in Table 1.

EXAMPLE 26

5.76 g of NaOH, (97%) was dissolved in 111.88 g water. 1.22 g Al(OH)₃,(27.9 wt.-% Al), was added to the sodium hydroxide solution. When thisbecame a solution, 37.5 g Ludox AS-40 was added. Next 0.30 g of thelayered material UZM-8 was added. The mixture was stirred vigorously for1-2 hours. The mixture was cooled to 0° C.-4° C. Separately, 0.89 g1,5-dibromopentane, (97%) was mixed with 7.36 g 1,4-dibromobutane,(99%), then 9.56 g 1-methylpyrrolidine, (97%) was added to form a secondmixture. The second mixture was added to the cooled mixture to createthe final reaction mixture. The final reaction mixture was vigorouslystirred and transferred to a 300 cc stirred autoclave. The finalreaction mixture was digested at 160° C. for 176 hours with stirring at100 rpm. The product was isolated by filtration. The product wasidentified as UZM-39 by XRD. Analytical results showed this material tohave the following molar ratios, Si/Al of 12.15, Na/Al of 0.15, N/Al of0.90, C/N of 7.59.

The product generated by this synthesis was calcined under flowing airat 600° C. for 6 hours. It was then ion exchanged four times with 1 Mammonium nitrate solution at 75° C. followed by a calcination at 500° C.under air for 2 hours to convert NH₄ ⁺ into H⁺. Analysis for thecalcined, ion-exchanged sample shows 38.6% Si, 2.85% Al, <0.01% Na.Analysis of the H⁺ form of this material by Rietveld XRD refinement gavethe results shown in Table 1.

EXAMPLE 27

5.76 g of NaOH, (97%) was dissolved in 111.88 g water. 1.22 g Al(OH)₃,(27.9 wt.-% Al), was added to the sodium hydroxide solution. When thisbecame a solution, 37.5 g Ludox AS-40 was added. Next, 0.30 g of thelayered material UZM-8 was added and the mixture was stirred vigorouslyfor 1-2 hours. The mixture was cooled to 0° C.-4° C. Separately, 1.78 g1,5-dibromopentane, (97%) was mixed with 6.54 g 1,4-dibromobutane,(99%), then 9.56 g 1-methylpyrrolidine, (97%) was added to form a secondmixture. The second mixture was added to the cooled mixture to createthe final reaction mixture. The final reaction mixture was vigorouslystirred and transferred to a 300 cc stirred autoclave. The finalreaction mixture was digested at 160° C. for 176 hours with stirring at100 rpm. The product was isolated by filtration. The product wasidentified as UZM-39 by XRD. Analytical results showed this material tohave the following molar ratios, Si/Al of 12.24, Na/Al of 0.107, N/Al of0.93, C/N of 6.91.

The product generated by this synthesis was calcined under flowing airat 600° for 6 hours. It was then ion exchanged four times with 1 Mammonium nitrate solution at 75° C. followed by a calcination at 500° C.under air for 2 hours to convert NH₄ ⁺ into Ft. Analysis for thecalcined, ion-exchanged sample shows 38.7% Si, 2.98% Al, 158 ppm Na witha BET surface area of 333 m²/g, pore volume of 0.201 cm³/g, andmicropore volume of 0.164 cm³/g. Analysis of the H⁺ form of thismaterial by Rietveld XRD refinement gave the results shown in Table 1.

EXAMPLE 28

5.76 g of NaOH, (97%) was dissolved in 111.88 g water. 1.22 g Al(OH)₃,(27.9 wt.-% Al), was added to the sodium hydroxide solution. When thisbecame a solution, 37.5 g Ludox AS-40 was added. Next, 0.30 g of thelayered material UZM-8 was added and the mixture was stirred vigorouslyfor 1-2 hours. The mixture was cooled to 0° C.-4° C. Separately, 2.67 g1,5-dibromopentane, (97%) was mixed with 5.73 g 1,4-dibromobutane,(99%), then 9.56 g 1-methylpyrrolidine, (97%) was added to form a secondmixture. The second mixture was added to the cooled mixture to createthe final reaction mixture. The final reaction mixture was vigorouslystirred and transferred to a 300 cc stirred autoclave. The finalreaction mixture was digested at 160° C. for 176 hours with stirring at100 rpm. The product was isolated by filtration. The product wasidentified as UZM-39 by XRD. The x-ray diffraction pattern is shown inFIG. 5. Analytical results showed this material to have the followingmolar ratios, Si/Al of 12.15, Na/Al of 0.108, N/Al of 0.86, C/N of 7.68.

The product generated by this synthesis was calcined under flowing airat 600° C. for 6 hours. It was then ion exchanged four times with 1 Mammonium nitrate solution at 75° C. followed by a calcination at 500°under air for 2 hours to convert NH₄ ⁺ into H. Analysis for thecalcined, ion-exchanged sample shows 38.7% Si, 2.98% Al, 79 ppm Na. Thex-ray diffraction pattern is shown in FIG. 6. Analysis of the H⁺ form ofthis material by Rietveld XRD refinement gave the results shown in Table1.

EXAMPLE 29

5.80 g of NaOH, (97%) was dissolved in 111.88 g water. 1.16 g Al(OH)₃,(29.32 wt.-% Al), was added to the sodium hydroxide solution. When thisbecame a solution, 37.5 g Ludox AS-40 was added. Next, 0.30 g of thelayered material UZM-8 was added and the mixture was stirred vigorouslyfor 1-2 hours. The mixture was cooled to 0° C.-4° C. Separately, 4.45 g1,5-dibromopentane, (97%) was mixed with 4.09 g 1,4-dibromobutane,(99%), then 9.56 g 1-methylpyrrolidine, (97%) was added to form a secondmixture. The second mixture was added to the cooled mixture to createthe final reaction mixture. The final reaction mixture was vigorouslystirred and transferred to a 300 cc stirred autoclave. The finalreaction mixture was digested at 160° C. for 224 hours with stirring at100 rpm. The product was isolated by filtration. The product wasidentified as UZM-39 by XRD. Analytical results showed this material tohave the following molar ratios, Si/Al of 11.75, Na/Al of 0.13, N/Al of0.86, C/N of 7.59.

The product generated by this synthesis was calcined under flowing airat 600° for 6 hours. It was then ion exchanged four times with 1 Mammonium nitrate solution at 75° C. followed by a calcination at 500° C.under air for 2 hours to convert NH₄ ⁺ into Ft. Analysis for thecalcined, ion-exchanged sample shows 40.1% Si, 3.32% Al, 90 ppm Na witha BET surface area of 305 m²/g, pore volume of 0.224 cm³/g, andmicropore volume of 0.146 cm³/g. Analysis of the H⁺ form of thismaterial by Rietveld XRD refinement gave the results shown in Table 1.

TABLE 1 Example # % TUN % IMF 3 100 0 6 95 5 13 83 17 17 46 54 18 36.563.5 23 24 76 24 0 100 25 19 81 26 58 42 27 30 70 28 13 87 29 8 92

EXAMPLE 30

To determine the quantities of TUN or IMF structure able to be detectedin a UZM-39 coherently grown composite structure material, a detectionlimit study was performed. A series of simulated diffraction patternswere electronically created from the observed diffraction patterns ofthe H⁺ forms of Example 3 and Example 24 products using JADE XRDanalysis software (available from Materials Data Incorporated). Mixturelevels ranged from 1% to 99% TUN and were created by scaling the smallerpercentage constituent to the required level, adding the patterns andsaving the composite pattern.

Rietveld analysis was able to quantify the level of IMF in the UZM-39coherently grown composite structure at the 10% or greater level,however visually, small percentages of IMF can be determined in samples(FIG. 12) largely consisting of TUN at the 5% or greater level fromintensity of peak at d-spacing of ˜9.46 A, while at higher levels, otherpeaks can be followed such as the increase in peak at d-spacing of ˜11.4A amongst others. In FIG. 12, spectrum 1 is 1% IMF, 99% TUN; spectrum 2is −3% IMF, 97% TUN; spectrum 3 is −5% IMF, 95% TUN; and spectrum 4 is−10% IMF, 90% TUN.

Rietveld analysis was able to quantify the level of TUN in the UZM-39coherently grown composite structure at the 10% or greater level,however FIG. 13 shows that, visually, small percentages of TUN can beseen in samples largely consisting of IMF at the 5% or greater levelfrom intensity of peak at d-spacing ˜12.25 A, while at higher levels,other peaks can be followed such as the increase in peak at d-spacing of−9.63 A amongst others. In FIG. 13, spectrum 1 is −1% TUN, 99% IMF;spectrum 2 is −3% TUN, 97% IMF; spectrum 3 is −5% TUN, 95% IMF; andspectrum 4 is −10% TUN, 90% IMF.

EXAMPLE 31

44.9 g of NaOH, (97%) was dissolved in 1122.3 g water. To this solutionwas added 10.8 g liquid sodium aluminate (22.9% Al₂O₃, 20.2% Na₂O)followed by 105.9 g Ultrasil VN3 (90% SiO₂, available from Evonik) toform a first mixture. Separately, 53.5 g 1,4-dibromobutane, (99%), wascombined with 62.6 g 1-methylpyrrolidine, (97%) to form a secondmixture. The second mixture was added to the first mixture to create thefinal reaction mixture. Last, 1 g of the layered material UZM-8 wasadded and the mixture was stirred vigorously for 1-2 hours beforetransferring to a 2 L stirred autoclave. The final reaction mixture wasdigested at 160° C. for 7 days while stirring at 200 rpm. The productwas isolated by filtration and identified as UZM-39 by XRD. Analyticalresults showed this material to have the following molar ratios, Si/Alof 12.40, Na/Al of 0.21, N/Al of 1.10, C/N of 7.06.

EXAMPLE 32

NaOH, Al(OH)₃, Ga(NO3)3.9H₂O, Ludox AS-40, 1,4-dibromobutane,1-methylpyrrolidine, water and layered material UZM-8 were combined toform a mixture of composition 0.5Al₂O₃:0.5 Ga₂O₃:65.4 SiO₂:24.6 Na₂O:9.9C₄Br₂:29.4 1-MP: 2636 H₂O and stirred vigorously for 1-2 hours beforetransferring to a 2 L stirred autoclave. The final reaction mixture wasdigested at 160° C. for 150 hours while stirring at 250 rpm. The productwas isolated by filtration and identified as UZM-39 by XRD. Analyticalresults showed this material to have the following molar ratios, Si/Alof 21.61, Si/Ga of 31.35, Si/(Al+Ga) of 12.79, Na/(Al+Ga) of 0.10,N/(Al+Ga) of 0.91, C/N of 7.39.

EXAMPLE 33

A UZM-39 containing a high quantity of TUN and low quantity of IMF inthe H+ form was loaded into a vertical steamer. The UZM-39 was exposedto 100% steam at 725° C. for 12 hours or 24 hours. The starting UZM-39had a BET surface area of 385 m²/g, pore volume of 0.248 cm³/g, andmicropore volume of 0.180 cm³/g. After 12 hours of steaming, the UZM-39was still identified as UZM-39 by XRD though the intensity of the first5 peaks had increased to strong, strong, very strong, strong and mediumrespectively. All other peaks were at positions and intensitiesdescribed in Table B. The material had a BET surface area of 331 m²/g,pore volume of 0.243 cm³/g, and micropore volume of 0.151 cm³/g. After24 hours of steaming, the UZM-39 was still identified as UZM-39 by XRDthough the intensity of the first 5 peaks had increased tomedium-strong, strong, strong, medium-strong and medium respectively.All other peaks were at positions and intensities described in Table B.The material had a BET surface area of 327 m²/g, pore volume of 0.241cm³/g, and micropore volume of 0.150 cm³/g.

EXAMPLE 34

A UZM-39 containing a high quantity of TUN and low quantity of IMF inthe H+ form was put into a round bottom flask containing 6N HNO₃ andoutfitted with a condenser and stirrer. The mixture containing UZM-39and HNO₃ was boiled at reflux for 8 or 16 h. The resulting material wasfiltered, washed and dried. XRD analysis showed the material to beUZM-39 consistent with Table B.

EXAMPLE 35

The product generated by the synthesis described in Example 1 was boundwith Si O₂ in a 75:25 weight ratio by combining 6.71 g Ludox AS-40, 8.31g UZM-39 and 10.79 g water. This mixture was then evaporated whilestirring to form the bound UZM-39/SiO₂. The bound material was thencalcined using a 2° C./minute ramp to 550° C., holding for 3 hours andthen cooling to room temperature. The 20 to 60 mesh fraction wasisolated and then used as the catalytic composite in a chemical reactionto form ethylbenzene and xylenes.

Benzene and propane were fed at a 2:1 mole ratio into a reactor at 410psig along with a hydrogen stream such that the hydrogen to hydrocarbonmole ratio was about 3.5. Multiple conditions where then set starting atabout 425° C. and 1.8 LHSV (Table 2 and Table 3 Column 1) and continuingto 485° C. and 1.8 LSVH (Table 2 and Table 3 Column 2); continuing againto 535° C. and 1.8 LHSV (Table 2 and Table 3 Column 3); continuing againto 535° C. and 3 LHSV (Table 2 and Table 3 Column 4); and finallycontinuing to 575° C. and 3 LHSV (Table 2 and Table 3 Column 5). Table 2shows the percent of benzene and propane conversion to other compounds.Table 3 shows the toluene plus C8 aromatic yield calculated bymultiplying selectivity to product with benzene conversion.

TABLE 2 Percent Conversion Column 1 Column 2 Column 3 Column 4 Column 5Benzene 7.43 16.15 26.19 22.90 26.79 Propane 57.58 61.58 81.35 68.7986.50

TABLE 3 Yield Column 1 Column 2 Column 3 Column 4 Column 5 Toluene plus1.9 4.9 14.7 12.5 13.4 C8 aromaticThe experiment was repeated using bound MFI catalyst as a comparativeexample. The process of the invention showed about 2-3 times theselectivity to C8 aromatics as compared to the results when using thebound MFI. Furthermore, the process of the invention resulted in verylittle formation of cyclohexane which in turn increases the purity of apotential benzene cut.

The invention claimed is:
 1. A process for dehydrocyclodimerizationcomprising contacting a feed comprising at least one aliphatichydrocarbon having from 2 to about 6 carbon atoms per molecule with amicroporous crystalline zeolitic catalytic composite atdehydrocyclodimerization conditions to produce at least one aromatichydrocarbon, the catalytic composite comprising at least a coherentlygrown composite of TUN and IMF zeotypes having a three-dimensionalframework of at least AlO₂ and SiO₂ tetrahedral units and an empiricalcomposition in the as synthesized and anhydrous basis expressed by anempirical formula of:Na_(n)M_(m) ^(k+)T_(t)Al_(1-x)E_(x)Si_(y)O_(z) where “n” is the moleratio of Na to (Al+E) and has a value from approximately 0.05 to 0.5, Mrepresents at least one metal selected from the group consisting ofzinc, Group 1 (IUPAC 1), Group 2 (IUPAC 2), Group 3 (IUPAC 3), and thelanthanide series of the periodic table, and any combination thereof,“m” is the mole ratio of M to (Al+E) and has a value from 0 to 0.5, “k”is the average charge of the metal or metals M, T is the organicstructure directing agent or agents derived from reactants R and Q whereR is an A,Ω-dihalogen substituted alkane having from 3 to 6 carbon atomsand Q is at least one neutral monoamine having 6 or fewer carbon atoms,“t” is the mole ratio of N from the organic structure directing agent oragents to (Al+E) and has a value of from about 0.5 to about 1.5, E is anelement selected from the group consisting of gallium, iron, boron andcombinations thereof, “x” is the mole fraction of E and has a value from0 to about 1.0, “y” is the mole ratio of Si to (Al+E) and varies fromgreater than 9 to about 25 and “z” is the mole ratio of O to (Al+E) andhas a value determined by the equation:z=(n+k·m+3+4·y)/2 and is characterized in that it has the x-raydiffraction pattern having at least the d-spacings and intensities setforth in Table A1: TABLE A1 2θ d (Å) I/Io % 7.17-7.21 12.25-12.31 vw-m 7.5-8.1* 11.78-10.91 w-m 8.88 9.95 m 9.17 9.63 w-m 12.47-12.627.09-7.00 w-m 17.7  5.01 vw-m 22.8-23.2 3.90-3.83 vs 23.39-23.493.80-3.78 m-s 25.01-25.31 3.56-3.52 m 28.74-29.25 3.10-3.05 w-m45.08-45.29 2.01-2.00 w. *composite peak consisting of multipleoverlapping reflections


2. The process of claim 1 wherein the coherently grown composite of TUNand IMF zeotypes is thermally stable up to a temperature of greater than600° C.
 3. The process of claim 1 wherein the coherently grown compositeof TUN and IMF zeotypes has a micropore volume as a percentage of totalpore volume of greater than 60%.
 4. The process of claim 1 wherein thecoherently grown composite of TUN and IMF zeotypes has a microporevolume as a percentage of total pore volume of greater than 90%.
 5. Theprocess of claim 1 wherein the dehydrocyclodimerization conditionsinclude a temperature from about 350° C. to about 650° C. (662° F. to1202° F.), a pressure from about 0 to about 300 psi(g) (0 to 2068kPa(g)), and a liquid hourly space velocity from about 0.2 to about 5hr⁻¹.
 6. The process of claim 1 wherein the catalytic composite furthercomprises gallium and a binder.
 7. The process of claim 1 wherein thedehydrocyclodimerization conditions include a temperature in the rangefrom about 400° C. to about 600° C. (752° F. to 1112° F.), a pressure inor about the range from about 0 to about 150 psi(g) (0 to 1034 kPa(g)),and a liquid hourly space velocity of between 0.5 to 3.0 hr⁻¹.
 8. Aprocess for dehydrocyclodimerization comprising contacting a feedcomprising at least one aliphatic hydrocarbon having from 2 to about 6carbon atoms per molecule with a microporous crystalline zeoliticcatalytic composite at dehydrocyclodimerization conditions to produce atleast one aromatic hydrocarbon, the catalytic composite comprising atleast a coherently grown composite of TUN and IMF zeotypes having athree-dimensional framework of at least AlO₂ and SiO₂ tetrahedral unitsand an empirical composition in the hydrogen form after calcination,ion-exchange and calcination and on an anhydrous basis expressed by anempirical formula ofM1_(a) ^(N+)Al_((1-x))E_(x)Si_(y′)O_(z″) and where M1 is at least oneexchangeable cation selected from the group consisting of alkali,alkaline earth metals, rare earth metals, zinc, ammonium ion, hydrogenion and combinations thereof, “a” is the mole ratio of M1 to (Al+E) andvaries from about 0.05 to about 50, “N” is the weighted average valenceof M1 and has a value of about +1 to about +3, E is an element selectedfrom the group consisting of gallium, iron, boron, and combinationsthereof, “x” is the mole fraction of E and varies from 0 to 1.0, y′ isthe mole ratio of Si to (Al+E) and varies from greater than about 9 tovirtually pure silica and z″ is the mole ratio of O to (Al+E) and has avalue determined by the equation:z″=(a·N+3+4·y′)/2 and is characterized in that it has the x-raydiffraction pattern having at least the d-spacings and intensities setforth in Table B1: TABLE B1 2θ d (Å) I/Io % 7.11-7.16 12.42-12.25 vw-m 7.5-8.1* 11.78-10.91 m-s  8.84 10.00  m-s 9.06-9.08 9.75-9.73 w-m  9.249.56 vw-m 12.46-12.53 7.10-7.06 w-m 22.56 3.94 vw-m 22.75-23.2 3.90-3.83vs 23.40 3.80 m-s 24.12-24.23 3.69-3.67 w-m 24.92-25.37 3.57-3.51 m28.71-29.27 3.11-3.05 w-m 45.32-45.36 2.00 w. *composite peak consistingof multiple overlapping reflections


9. The process of claim 8 wherein the coherently grown composite of TUNand IMF zeotypes is thermally stable up to a temperature of greater than600 C.
 10. The process of claim 8 wherein the coherently grown compositeof TUN and IMF zeotypes has a micropore volume as a percentage of totalpore volume of greater than 60%.
 11. The process of claim 8 wherein thecoherently grown composite of TUN and IMF zeotypes has a microporevolume as a percentage of total pore volume of greater than 90%.
 12. Theprocess of claim 8 wherein the dehydrocyclodimerization conditionsinclude a temperature from about 350° C. to about 650° C. (662° F. to1202° F.), a pressure from about 0 to about 300 psi(g) (0 to 2068kPa(g)), and a liquid hourly space velocity from about 0.2 to about 5hr⁻¹.
 13. The process of claim 8 wherein the catalytic composite furthercomprises gallium and a binder.
 14. The process of claim 8 wherein thedehydrocyclodimerization conditions include a temperature in the rangefrom about 400° C. to about 600° C. (752° F. to 1112° F.), a pressure inor about the range from about 0 to about 150 psi(g) (0 to 1034 kPa(g)),and a liquid hourly space velocity of between 0.5 to 3.0 hr⁻¹.
 15. Theprocess of claim 8 wherein the at least one aromatic hydrocarbon isbenzene, toluene, or a xylene.
 16. The process of claim 8 wherein thefeed is selected from the group consisting of C3 and/or C4 derivedstreams from FCC cracked products, light gasses from a delayed cokingprocess, and liquefied petroleum gas streams.
 17. The process of claim 8wherein the product stream further comprises light hydrocarbons whichare separated from the product stream and recycled to the contactingwith a catalytic composite step or wherein the product stream comprisesbenzene and xylenes the process further comprising separating thebenzene and recycling the separated benzene to the contacting with acatalytic composite step.
 18. The process of claim 8 wherein thecatalytic composite is located in one or more catalyst zones arranged inseries or parallel configuration, and wherein the catalytic compositemay be in fixed beds or fluidized beds.